JPWO2020032131A1 - Methods for producing compounds, thiol generators, compositions, cured products and cured products - Google Patents

Abstract

An object of the present invention is to provide a compound capable of forming a composition having excellent patterning accuracy and heat resistance. The present invention is a compound represented by the following general formula (A). (In the formula, R1 is an aliphatic group having 1 to 40 monovalent carbon atoms, an aromatic hydrocarbon ring-containing group having 6 to 35 monovalent carbon atoms, and a complex having 2 to 35 monovalent carbon atoms. It represents a ring-containing group or a silyl group having a monovalent carbon number of 0 to 40, and X is an aliphatic group having the same number of valences as n and having 1 to 40 carbon atoms, and an aromatic having 6 to 35 carbon atoms. It represents a group hydrocarbon ring-containing group or a heterocyclic ring-containing group having 2 to 35 carbon atoms, and n represents an integer of 2 or more and 10 or less.)

Description

The present invention relates to a compound capable of forming a composition having excellent patterning accuracy and heat resistance.

The thiol compound can cause a reaction such as a thiol-ene reaction (also referred to as an ene-thiol reaction) with an acrylic monomer or the like.
Further, such a polymerization reaction proceeds even in the absence of a polymerization initiator.
Therefore, by adding the thiol compound together with the polymerization initiator to the acrylic monomer, the polymerization reaction of the acrylic monomer and the like by the polymerization initiator and the reaction of the acrylic monomer and the like by the thiol compound can be carried out at the same time.
Utilizing such properties, thiol compounds are used for improving the sensitivity of photocurable compositions (for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2006-154774

As a method for forming a patterned cured product using a photocurable composition, the coating film of the photocurable composition is exposed in a pattern, the uncured coating film is removed with a developing solution, and then heat treatment is performed. There is a known method of performing (post-baking).
When a thiol compound as described in Patent Document 1 is added to a photocurable composition to form a patterned cured product, a patterned cured product having excellent heat resistance such as less shrinkage during the heat treatment is obtained. be able to.
However, there is a problem that the patterning accuracy is lowered by adding the thiol compound.
In addition, the present inventors have studied increasing the amount of the polymerization initiator added in order to improve the heat resistance and the like. However, although the heat resistance can be improved as in the case of adding the thiol compound, there is a problem that the patterning accuracy is lowered.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a compound capable of forming a composition having excellent patterning accuracy and heat resistance.

As a result of diligent studies to solve the above problems, the present inventors suppress the progress of the reaction by the thiol compound such as the thiol-ene reaction until after the completion of patterning, and the above reaction can proceed after the completion of patterning. It has been found that by using a compound, it is possible to form a composition excellent in both patterning accuracy and heat resistance.
The present inventors have completed the present invention based on these findings.

That is, the present invention is a compound represented by the following general formula (A) (hereinafter, also referred to as “Compound A”).

（式中、Ｒ^１は、一価の炭素原子数１〜４０の脂肪族基、一価の炭素原子数６〜３５の芳香族炭化水素環含有基、一価の炭素原子数２〜３５の複素環含有基又は一価の炭素原子数０〜４０のシリル基を表し、
Ｘは、ｎと同数の価数を有する炭素原子数１〜４０の脂肪族基、炭素原子数６〜３５の芳香族炭化水素環含有基又は炭素原子数２〜３５の複素環含有基を表し、
前記脂肪族基、芳香族炭化水素環含有基、複素環含有基及びシリル基中のメチレン基の１つ又は２つ以上は、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｏ−、−Ｓ−ＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｓ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＮＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＮＨ−、−ＮＲ’−、−Ｓ−Ｓ−若しくは−ＳＯ_２−から選ばれた基で置き換えられている場合があるか、又は酸素原子が隣り合わない条件でこれらの基を組み合わせた基で置き換えられている場合があり、
ｎは２以上１０以下の整数を表す。）

(In the formula, R ¹ is an aliphatic group having a monovalent carbon atom number of 1 to 40, an aromatic hydrocarbon ring-containing group having a monovalent carbon atom number of 6 to 35, and a monovalent carbon atom number of 2 to 35. Represents a heterocyclic group or a silyl group having a monovalent carbon number of 0 to 40.
X represents an aliphatic group having 1 to 40 carbon atoms having the same number of valences as n, an aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 35 carbon atoms. ,
One or more of the methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocyclic group and silyl group are -O-, -S-, -CO- and -O-CO-. , -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-,- Is it sometimes replaced with a group selected from NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -S-S- or -SO _2-? , Or may be replaced by a group that combines these groups under the condition that the oxygen atoms are not adjacent to each other.
n represents an integer of 2 or more and 10 or less. )

According to the present invention, the compound A can form a composition having excellent patterning accuracy and heat resistance by having the above structure.

In the present invention, the compound A is preferably a compound represented by the following general formulas (A1), (A2), (A3), (A4), (A5) or (A6). This is because, since the compound A is a compound having the above structure, it becomes a compound capable of forming a composition excellent in patterning accuracy and heat resistance, and in particular, a composition excellent in heat resistance can be formed.

（式中、Ｒ^１１及びＲ^１２は、それぞれ独立に、下記一般式（１０１）を表し、
Ｌ^１１及びＬ^１２は、炭素原子数１〜１０のアルキレン基を表し、
ａ１は、１〜２０の整数を表し、
Ｒ^２１、Ｒ^２２及びＲ^２３は、それぞれ独立に、下記一般式（１０１）又は（１０２）を表し、
Ｒ^２１、Ｒ^２２及びＲ^２３のうち、いずれか２つ以上が、下記一般式（１０１）であり、
Ｌ^２１、Ｌ^２２及びＬ^２３は、炭素原子数１〜１０のアルキレン基を表し、
Ｒ^２４は、水素原子又は一価の炭素原子数１〜４０の脂肪族基を表し、
Ｒ^３１、Ｒ^３２、Ｒ^３３及びＲ^３４は、それぞれ独立に、下記一般式（１０１）又は（１０２）を表し、
Ｒ^３１、Ｒ^３２、Ｒ^３３及びＲ^３４のうち、いずれか２つ以上が、下記一般式（１０１）であり、
Ｌ^３１、Ｌ^３２、Ｌ^３３及びＬ^３４は、炭素原子数１〜１０のアルキレン基を表し、
Ｒ^４１、Ｒ^４２、Ｒ^４３、Ｒ^４４、Ｒ^４５及びＲ^４６は、それぞれ独立に、下記一般式（１０１）又は（１０２）を表し、
Ｒ^４１、Ｒ^４２、Ｒ^４３、Ｒ^４４、Ｒ^４５及びＲ^４６のうち、いずれか２つ以上が、下記一般式（１０１）であり、
Ｌ^４１、Ｌ^４２、Ｌ^４３、Ｌ^４４、Ｌ^４５及びＬ^４６は、炭素原子数１〜１０のアルキレン基を表し、
Ｒ^５１、Ｒ^５２及びＲ^５３は、それぞれ独立に、下記一般式（１０１）又は（１０２）を表し、
Ｒ^５１、Ｒ^５２及びＲ^５３のうち、いずれか２つ以上が、下記一般式（１０１）であり、
Ｌ^５１、Ｌ^５２及びＬ^５３は、炭素原子数１〜１０のアルキレン基を表し、
Ｒ^６１、Ｒ^６２、Ｒ^６３及びＲ^６４は、それぞれ独立に、下記一般式（１０１）又は（１０２）を表し、
Ｒ^６１、Ｒ^６２、Ｒ^６３及びＲ^６４のうち、いずれか２つ以上が、下記一般式（１０１）であり、
Ｌ^６１、Ｌ^６２、Ｌ^６３及びＬ^６４は、炭素原子数１〜１０のアルキレン基を表し、
Ｒ^６５及びＲ^６６は、それぞれ独立に、水素原子又は一価の炭素原子数１〜４０の脂肪族基を表し、
前記脂肪族基中のメチレン基の１つ又は２つ以上は、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｏ−、−Ｓ−ＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｓ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＮＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＮＨ−、−ＮＲ’−、−Ｓ−Ｓ−若しくは−ＳＯ_２−から選ばれた基で置き換えられている場合があるか、又は酸素原子が隣り合わない条件でこれらの基を組み合わせた基で置き換えられている場合がある。）

(In the formula, R ¹¹ and R ¹² independently represent the following general formula (101).
L ¹¹ and L ¹² represent an alkylene group having 1 to 10 carbon atoms.
a1 represents an integer of 1 to 20 and represents
R ²¹ , R ²² and R ²³ independently represent the following general formula (101) or (102), respectively.
Any two or more of R ²¹ , R ²² and R ²³ have the following general formula (101).
L ²¹ , L ²² and L ²³ represent an alkylene group having 1 to 10 carbon atoms.
R ²⁴ represents an aliphatic group having a hydrogen atom or a monovalent carbon atom number of 1 to 40.
R ³¹ , R ³² , R ³³ and R ³⁴ independently represent the following general formula (101) or (102).
Any two or more of R ³¹ , R ³² , R ^33, and R ³⁴ have the following general formula (101).
L ³¹ , L ³² , L ³³ and L ³⁴ represent an alkylene group having 1 to 10 carbon atoms.
R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ independently represent the following general formula (101) or (102), respectively.
Any two or more of R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ is the following general formula (101).
L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ and L ⁴⁶ represent an alkylene group having 1 to 10 carbon atoms.
R ⁵¹ , R ⁵² and R ⁵³ independently represent the following general formula (101) or (102), respectively.
Any two or more of R ⁵¹ , R ^52, and R ⁵³ have the following general formula (101).
L ⁵¹ , L ⁵² and L ⁵³ represent an alkylene group having 1 to 10 carbon atoms.
R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ independently represent the following general formula (101) or (102).
Any two or more of R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ is the following general formula (101).
L ⁶¹ , L ⁶² , L ⁶³ and L ⁶⁴ represent an alkylene group having 1 to 10 carbon atoms.
R ⁶⁵ and R ⁶⁶ each independently represent a hydrogen atom or an aliphatic group having 1 to 40 monovalent carbon atoms.
One or more of the methylene groups in the aliphatic group are -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-,-. S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -O- It may have been replaced with a group selected from CO-NH-, -NR'-, -S-S- or -SO _2- , or these groups were combined under the condition that the oxygen atoms were not adjacent to each other. May have been replaced by a group. )

（式中、Ｒ^１は、一価の炭素原子数１〜４０の脂肪族基、一価の炭素原子数６〜３５の芳香族炭化水素環含有基、一価の炭素原子数２〜３５の複素環含有基又は一価の炭素原子数０〜４０のシリル基を表し、
＊は、結合箇所を表し、
前記脂肪族基、芳香族炭化水素環含有基、複素環含有基及びシリル基中のメチレン基の１つ又は２つ以上は、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｏ−、−Ｓ−ＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｓ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＮＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＮＨ−、−ＮＲ’−、−Ｓ−Ｓ−若しくは−ＳＯ_２−から選ばれた基で置き換えられている場合があるか、又は酸素原子が隣り合わない条件でこれらの基を組み合わせた基で置き換えられている場合がある。）

(In the formula, R ¹ is an aliphatic group having a monovalent carbon atom number of 1 to 40, an aromatic hydrocarbon ring-containing group having a monovalent carbon atom number of 6 to 35, and a monovalent carbon atom number of 2 to 35. Represents a heterocyclic group or a silyl group having a monovalent carbon number of 0 to 40.
* Indicates the joint location
One or more of the methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocyclic group and silyl group are -O-, -S-, -CO- and -O-CO-. , -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-,- Is it sometimes replaced with a group selected from NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -S-S- or -SO _2-? , Or the oxygen atoms may be replaced with a combined group of these groups under the condition that they are not adjacent to each other. )

In the present invention, ^{all of R 21} , R ²² and R ^{23 in} the general formula (A2) are independently the general formula (101), and R ³¹ , R in the general formula (A3). ³² , R ³³ and R ³⁴ are all independently of the above general formula (101), and of R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ^{46 in} the above general formula (A4). All of them are independently of the above general formula (101), and ^{all of R 51} , R ⁵² and R ^{53 of} the above general formula (A5) are independently of the above general formula (101). ^{It is preferable that all of R 61} , R ⁶² , R ⁶³ and R ^{64 in} the general formula (A6) are independently of the general formula (101).
R ²¹ , R ²² , R ²³ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁵¹ , R ⁵² , R ⁵³ , R ^{This is because, when 61} , R ⁶² , R ⁶³ and R ⁶⁴ are the above-mentioned groups, the compound A can form a composition excellent in patterning accuracy and heat resistance.

In the present invention, the compound A is preferably a compound represented by the general formula (A4) or (A6). This is because the compound A can form a composition excellent in patterning accuracy and heat resistance.

In the present invention, the above R ¹ is a monovalent aliphatic group having 1 to 40 carbon atoms or a monovalent group in which the methylene group at the end on the sulfur atom side is substituted with -CO-O- or -CO-NR-. It is preferably an aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms. This is because when the R ¹ is the above-mentioned group, the compound A can form a composition excellent in patterning accuracy and heat resistance.

The present invention is a thiol generator containing the above compounds.

According to the present invention, the inclusion of the compound A makes it possible for the thiol generator to form a composition having excellent patterning accuracy and heat resistance.

The present invention is a composition comprising a compound represented by the following general formula (A) and a thiol-reactive polymerizable component (hereinafter, may be referred to as polymerizable component B).

（式中、Ｒ^１は、一価の炭素原子数１〜４０の脂肪族基、一価の炭素原子数６〜３５の芳香族炭化水素環含有基、一価の炭素原子数２〜３５の複素環含有基又は一価の炭素原子数０〜４０のシリル基を表し、
Ｘは、ｎと同数の価数を有する炭素原子数１〜４０の脂肪族基、炭素原子数６〜３５の芳香族炭化水素環含有基又は炭素原子数２〜３５の複素環含有基を表し、
前記脂肪族基、芳香族炭化水素環含有基、複素環含有基及びシリル基中のメチレン基の１つ又は２つ以上は、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｏ−、−Ｓ−ＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｓ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＮＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＮＨ−、−ＮＲ’−、−Ｓ−Ｓ−若しくは−ＳＯ_２−から選ばれた基で置き換えられている場合があるか、又は酸素原子が隣り合わない条件でこれらの基を組み合わせた基で置き換えられている場合があり、
ｎは２以上１０以下の整数を表す。）

(In the formula, R ¹ is an aliphatic group having a monovalent carbon atom number of 1 to 40, an aromatic hydrocarbon ring-containing group having a monovalent carbon atom number of 6 to 35, and a monovalent carbon atom number of 2 to 35. Represents a heterocyclic group or a silyl group having a monovalent carbon number of 0 to 40.
X represents an aliphatic group having 1 to 40 carbon atoms having the same number of valences as n, an aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 35 carbon atoms. ,
One or more of the methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocyclic group and silyl group are -O-, -S-, -CO- and -O-CO-. , -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-,- Is it sometimes replaced with a group selected from NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -S-S- or -SO _2-? , Or may be replaced by a group that combines these groups under the condition that the oxygen atoms are not adjacent to each other.
n represents an integer of 2 or more and 10 or less. )

According to the present invention, since the composition contains the compound A, the composition is excellent in patterning accuracy and heat resistance.

In the present invention, the thiol-reactive polymerizable component preferably contains a radically polymerizable compound. This is because the above composition has an excellent curing rate. Further, it is easy to crosslink using the compound A.

The present invention is a cured product of the above composition.

According to the present invention, since the cured product contains the compound A, it has excellent patterning accuracy and heat resistance.

The present invention provides a method for producing a cured product, which comprises a step of cross-linking the above-mentioned polymerizable components having thiol reactivity with the compound represented by the above-mentioned general formula (A).

According to the present invention, a cured product having excellent heat resistance can be produced by cross-linking the polymerizable component B with the compound A.

In the present invention, it is preferable to have a step of polymerizing the above-mentioned polymerizable components having thiol reactivity. This is because the patterning accuracy and heat resistance are improved.

According to the present invention, it is possible to provide a compound capable of forming a composition having excellent patterning accuracy and heat resistance.

An example of an optical microscope observation image when the pattern is wrinkled. An example of an SEM observation image when the pattern is wrinkled. An example of an optical microscope observation image when the pattern is not wrinkled. An example of an SEM observation image when the pattern is not wrinkled.

The present invention relates to a compound, a thiol generator using the compound, a composition, a cured product, and a method for producing a cured product.
Hereinafter, the compound, the thiol generator, the composition, the cured product, and the method for producing the cured product of the present invention will be described in detail.

A. Compounds First, the compounds of the present invention will be described.
The compound of the present invention is a compound represented by the following general formula (A) (hereinafter, also referred to as “Compound A”).

（式中、Ｒ^１は、一価の炭素原子数１〜４０の脂肪族基、一価の炭素原子数６〜３５の芳香族炭化水素環含有基、一価の炭素原子数２〜３５の複素環含有基又は一価の炭素原子数０〜４０のシリル基を表し、
Ｘは、ｎと同数の価数を有する炭素原子数１〜４０の脂肪族基、炭素原子数６〜３５の芳香族炭化水素環含有基又は炭素原子数２〜３５の複素環含有基を表し、
前記脂肪族基、芳香族炭化水素環含有基、複素環含有基及びシリル基中のメチレン基の１つ又は２つ以上は、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｏ−、−Ｓ−ＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｓ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＮＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＮＨ−、−ＮＲ’−、−Ｓ−Ｓ−若しくは−ＳＯ_２−から選ばれた基で置き換えられている場合があるか、又は酸素原子が隣り合わない条件でこれらの基を組み合わせた基で置き換えられている場合があり、
ｎは２以上１０以下の整数を表す。）

(In the formula, R ¹ is an aliphatic group having a monovalent carbon atom number of 1 to 40, an aromatic hydrocarbon ring-containing group having a monovalent carbon atom number of 6 to 35, and a monovalent carbon atom number of 2 to 35. Represents a heterocyclic group or a silyl group having a monovalent carbon number of 0 to 40.
X represents an aliphatic group having 1 to 40 carbon atoms having the same number of valences as n, an aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 35 carbon atoms. ,
One or more of the methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocyclic group and silyl group are -O-, -S-, -CO- and -O-CO-. , -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-,- Is it sometimes replaced with a group selected from NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -S-S- or -SO _2-? , Or may be replaced by a group that combines these groups under the condition that the oxygen atoms are not adjacent to each other.
n represents an integer of 2 or more and 10 or less. )

According to the present invention, the compound A can form a composition having excellent patterning accuracy and heat resistance by having the above structure.
The reason why the compound A can form a composition having excellent patterning accuracy and heat resistance by having the above structure is presumed as follows.

Since the thiol group of the compound A is ^{protected by R 1} , the polymerizable component B is used until after the completion of patterning, for example, after the step of polymerizing the polymerizable components B in the composition and the step of developing the compound B. The progress of the cross-linking reaction that bridges each other can be suppressed.
As a result, the compound A can suppress the progress of curing of the composition beyond a desired pattern during the polymerization step, the development step, and the like, and has excellent patterning accuracy.
Further, the compound A can carry out a cross-linking reaction for cross-linking the polymerizable components B by desorbing the ^{protecting group R 1} and generating two or more thiol groups by, for example, heat treatment. Then, the cross-linking density of the cured product is improved by the progress of the cross-linking reaction.
As a result, it is possible to obtain a cured product having less shrinkage during heat treatment such as post-baking, that is, a cured product having excellent heat resistance.
From the above, the compound A can form a composition having excellent patterning accuracy and heat resistance.
Further, since the cross-linking reaction proceeds even in the absence of the polymerization initiator, it can proceed not only on the surface of the cured product but also in a deep part deep in the thickness direction from the surface of the cured product. As a result, the difference in cross-linking density between the front surface side and the back surface side of the cured product becomes small, and for example, the occurrence of warpage and wrinkles due to the difference in cross-linking density is suppressed.
Further, due to the effect of excellent patterning accuracy, the above-mentioned compound A facilitates the formation of a patterned cured product having a narrow line width, and also has an excellent exposure margin with little variation in the line width due to variations in the exposure time. The composition can be easily obtained.
Further, due to the effect that a cured product having excellent heat resistance can be obtained, the compound A can be used for forming a member that requires heat treatment as a curing treatment, thereby forming a member having a thick film thickness. It will be easy.
Furthermore, by simultaneously achieving the effect of facilitating the formation of a patterned cured product having a narrow line width and the effect of facilitating the formation of a site agent having a thick film thickness, for example, a fine pattern with a high aspect ratio can be easily formed. The formation of the cured product becomes easy. Further, when forming a cured product having a high aspect ratio, the coating film of the composition can be easily thinned, and for example, the cost can be easily reduced.
Further, as a method of forming a cured product having a high aspect ratio without using the compound A, a method of reducing the exposure amount can be considered. In this case, it is expected that the degree of curing of the cured product will decrease and the development margin will decrease as a result. On the other hand, when the compound A is used, it is not necessary to reduce the exposure amount due to the effect that it is easy to form a patterned cured product having a high aspect ratio, and the patterned product has a high development margin. A cured product can be easily obtained.
From the above, the above-mentioned compound A is excellent in patterning accuracy and heat resistance by being used in a composition for forming a patterned cured product, and is a patterned cured product having a narrow line width and a patterned cured product having a high aspect ratio. A composition suitable for the formation of the above can be obtained. Further, the compound A is excellent in exposure margin and development margin at the time of forming a patterned cured product, and a composition excellent in process passability can be obtained.
Further, by adding the compound A to the curable composition, it is possible to improve the resistance of the cured product to an alkaline developer during development after the curing treatment by exposure. Therefore, the composition containing the above compound can stably form a patterned cured product with respect to variations in the alkaline development time. Therefore, it is possible to make the development margin excellent in the developing process, and from this result, it becomes easy to make the patterning accuracy excellent.
From the above, the above-mentioned compound A is exhibited at the time of carrying out the excellent patterning accuracy exhibited in the polymerization process, the excellent development margin exhibited in the developing process, and the subsequent heat treatment process such as the post-baking process. The excellent heat resistance can be exhibited in a well-balanced manner, and the patterning accuracy and heat resistance are excellent as a whole. Therefore, the compound A is particularly suitable for, for example, a curable composition for forming a patterned cured product.

The ^{monovalent aliphatic group having 1 to 40 carbon atoms represented by R 1} may be any group that does not contain an aromatic hydrocarbon ring and a heterocycle. For example, an alkyl having 1 to 40 carbon atoms. One or more of a group, an alkenyl group having 2 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, a cycloalkylalkyl group having 4 to 40 carbon atoms, and hydrogen atoms of these groups will be described later. Examples thereof include groups substituted with the substituents to be used.
In the present invention, the aliphatic group refers to a group obtained by removing an arbitrary atom from an aliphatic compound.

Examples of the alkyl group having 1 to 40 carbon atoms include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-pentyl, tert-pentyl, cyclopentyl and hexyl. , 2-Hexyl, 3-Hexyl, Cyclohexyl, 4-Methylcyclohexyl, Heptyl, 2-Heptyl, 3-Heptyl, iso-Heptyl, tert-Heptyl, 1-octyl, iso-octyl, tert-octyl, adamantyl, etc. Be done.

Examples of the alkenyl group having 2 to 40 carbon atoms include vinyl, ethylene, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl and 5-hexenyl. , 2-Heptenyl, 3-Heptenyl, 4-Heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl and 4,8,12-tetradecatrienylallyl.

The cycloalkyl group having 3 to 40 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 40 carbon atoms. Examples of the cycloalkyl group having 3 to 40 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene and bicyclo [1. 1.1] Pentanyl and the like can be mentioned.

The cycloalkylalkyl group having 4 to 40 carbon atoms means a group having 4 to 40 carbon atoms in which the hydrogen atom of the alkyl group is replaced with a cycloalkyl group. Examples of the cycloalkylalkyl group having 4 to 40 carbon atoms include cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, and 2-cyclononylethyl. , 2-Cyclodecylethyl, 3-adamantylpropyl, decahydronaphthylpropyl and the like.

The aromatic hydrocarbon ring-containing group having a carbon number of 6 to 35 monovalent represented by R ^1, may be one containing an aromatic hydrocarbon ring, for example, aryl having a carbon number of 6 to 35 Examples thereof include a group, an arylalkyl group having 7 to 35 carbon atoms, and a group in which one or more of the hydrogen atoms of these groups are substituted with a substituent described later.
Further, the aromatic hydrocarbon ring-containing group usually does not contain a heterocyclic group.

Examples of the aryl group having 6 to 35 carbon atoms include phenyl, naphthyl, anthracenyl and the like.

Examples of the arylalkyl group having 7 to 35 carbon atoms include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl group and the like.

Examples of the heterocyclic ring-containing group having a carbon number of 2-35 monovalent represented by R ^1, may be one containing heterocycles include pyridyl, pyrimidyl, pyridazinyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolyl, Kinolyl, isoquinolyl, imidazolyl, benzoimidazolyl, triazolyl, frills, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolidine, benzoxazolidine, isothiazolidine, isooxazolidine, indolyl, 2-pyrrolidinone-1-yl , 2-Piperidin-1-yl, 2,4-dioxyimidazolidine-3-yl, 2,4-dioxyoxazolidine-3-yl and one or more of the hydrogen atoms of these groups will be described later. Examples thereof include a group substituted with a substituent.

The ^{silyl group having a monovalent number of carbon atoms 0 to 40 represented by R 1} may be any one containing a silicon atom, and the hydrogen atom is substituted with an unsubstituted silyl group and the hydrogen atom is substituted with another substituent. Examples thereof include a substituted silyl group and a group in which one or two or more hydrogen atoms of these groups are substituted with a substituent described later.
Examples of the substituted silyl group include silyl groups such as monoalkylsilyl group, monoarylsilyl group, dialkylsilyl group, diarylsilyl group, trialkylsilyl group, triarylsilyl group, monoalkyldiarylsilyl group and dialkylmonoarylsilyl group. Can be mentioned.
Examples of the monoalkylsilyl group include a monomethylsilyl group, a monoethylsilyl group, a monobutylsilyl group, a monoisopropylsilyl group, a monodecanesilyl group, a monoicosansilyl group, and a monotriacontanesilyl group.
Examples of the monoarylsilyl group include a monophenylsilyl group, a monotrilsilyl group, a mononaphthylsilyl group, a monoanthrylsilyl group and the like.
Examples of the dialkylsilyl group include a dimethylsilyl group, a diethylsilyl group, a dimethylethylsilyl group, a diisopropylsilyl group, a dibutylsilyl group, a dioctylsilyl group, a didecanesilyl group and the like.
Examples of the diarylsilyl group include a diphenylsilyl group and a ditrilsilyl group.
Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a dimethylethylsilyl group, a triisopropylsilyl group, a tributylsilyl group, a trioctylsilyl group and the like.
Examples of the triarylsilyl group include a triphenylsilyl group and a tritrylsilyl group.
Examples of the monoalkyldiarylsilyl group include a methyldiphenylsilyl group and an ethyldiphenylsilyl group.
Examples of the dialkyl monoarylsilyl group include a dimethylphenylsilyl group and a methylethylphenyl group.

The aliphatic group represented by R ^1, an aromatic hydrocarbon ring-containing group, one or two or more methylene groups in the heterocyclic ring-containing group and silyl group, -O -, - S -, - CO -, - O -CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH Even if it is replaced with a group selected from-, -NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -SS- or -SO _2- Well, or may be replaced with a group combining these groups under the condition that the oxygen atoms are not adjacent to each other.
That is, in R ¹ , one or more of the methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocycle-containing group and silyl group are -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO A group selected from -NH-, -NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -SS- or -SO _2- , or an oxygen atom. It may be a group having a structure in which these groups are replaced with a group in which these groups are combined under the condition that the groups are not adjacent to each other.
The R'represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and as the alkyl group having 1 to 8 carbon atoms, a predetermined number of carbon atoms among the alkyl groups represented by ^{R 1 is used.} There are things that meet.

Aliphatic group in the above R ^1, an aromatic hydrocarbon ring-containing group, each functional group such as a heterocyclic ring-containing group and silyl group, unless otherwise specified, no substituents unsubstituted or substituted group Is a group that has.
Substituents that substitute one or more hydrogen atoms in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocyclic group and silyl group, more specifically, the above-mentioned alkyl group and alkenyl group. , Cycloalkyl group, cycloalkylalkyl group, aryl group, arylalkyl group, heterocyclic group and silyl group as substituents for substituting one or more hydrogen atoms include fluorine, chlorine, bromine and iodine. Halogen atoms such as: acetyl, 2-chloroacetyl, propionyl, octanoyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, Acyl group such as n-octadecyloxycarbonyl, carbamoyl; acyloxy group such as acetyloxy, benzoyloxy; amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino , Truidino, Anisidino, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino, N, N- Dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, Substituent amino groups such as sulfamoylamino, N, N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino; sulfonamide group, sulfonyl group, carboxyl group, cyano group, sulfo group, hydroxyl group, nitro Examples thereof include a group, an imide group, a carbamoyl group, a sulfonamide group, a phosphonic acid group, a phosphoric acid group or a carboxyl group, a sulfo group, a phosphonic acid group, a salt of a phosphoric acid group and the like.
The number of carbon atoms when the hydrogen atom of the aliphatic group having 1 to 40 carbon atoms is substituted refers to the number of carbon atoms after the hydrogen atom is substituted, and before the hydrogen atom is substituted. It does not refer to the number of carbon atoms in. Hereinafter, the same applies when the hydrogen atom in the other group is substituted.
The number of carbon atoms when the methylene group in the aliphatic group having 1 to 40 carbon atoms is substituted refers to the number of carbon atoms after the methylene group is substituted, and the methylene group is substituted. It does not refer to the previous number of carbon atoms. Hereinafter, the same applies when the methylene group in the other groups is substituted.

From the viewpoint of obtaining a compound capable of forming a composition excellent in patterning accuracy and heat resistance, the above R ¹ has an aliphatic group having a monovalent carbon number of 1 to 40 and a monovalent carbon number of 6 to 40. 35 aromatic hydrocarbon ring-containing groups, heterocyclic ring-containing groups having 2-35 monovalent carbon atoms, or silyl groups having monovalent carbon atoms of 0 to 40 have a methylene group at the sulfur atom-side terminal of -CO-O. An aliphatic group having 1 to 40 monovalent carbon atoms, an aromatic hydrocarbon ring-containing group having 6 to 35 monovalent carbon atoms, and a monovalent carbon atom number replaced by − or −CO-NH−. It is preferably a heterocycle-containing group of 2 to 35 or a silyl group having a monovalent number of carbon atoms of 0 to 40.
That is, R ¹ is an aliphatic group having a monovalent carbon atom number of 1 to 40, an aromatic hydrocarbon ring-containing group having a monovalent carbon atom number of 6 to 35, and a complex having a monovalent carbon atom number of 2 to 35. It is preferable that the ring-containing group or the methylene group at the sulfur atom-side terminal of the silyl group having a monovalent number of carbon atoms of 0 to 40 is a group having a structure in which -CO-O- or -CO-NH- is replaced.

The above R ¹ is an aliphatic group having a monovalent carbon atom number of 1 to 40 or a monovalent carbon atom number of 6 to 35 in which the sulfur atom side terminal is substituted with -CO-O- or -CO-NH-. It is more preferably an aromatic hydrocarbon ring-containing group, and further, an alkyl group having 1 to 40 carbon atoms or an alkyl group having 1 to 40 carbon atoms in which the sulfur atom side terminal is substituted with -CO-O- or -CO-NH-. It is preferably 6 to 35 arylalkyl groups. In particular, when an alkyl group having 1 to 40 carbon atoms in which the sulfur atom side terminal is substituted with -CO-O-, that is, -CO-O-R "(R" has a substituent. An arylalkyl group having 6 to 35 carbon atoms, that is, an arylalkyl group having 6 to 35 carbon atoms, that is, a group represented by an alkyl group having 1 to 39 carbon atoms) or an arylalkyl group having a sulfur atom side substituted with -CO-NH-, that is, -CO-NH. -R''''(R'''' is a group represented by an aryl group having 6 to 34 carbon atoms or an arylalkyl group having 6 to 34 carbon atoms which may have a substituent). Is preferable, and in particular, it is preferable that the group is represented by −CO—OR ″. This is because when the R ¹ is the above-mentioned group, the compound A can form a composition excellent in patterning accuracy and heat resistance.
That is, in the above R ¹ , the methylene group at the sulfur atom side terminal of the aliphatic group having a monovalent carbon atom number of 1 to 40 or the aromatic hydrocarbon ring-containing group having a monovalent carbon atom number of 6 to 35 is -CO. It is more preferably a group having a structure substituted with −O− or −CO—NH−, and further, a sulfur atom-side terminal of an alkyl group having 1 to 40 carbon atoms or an arylalkyl group having 6 to 35 carbon atoms. The methylene group of is preferably a group having a structure substituted with -CO-O- or -CO-NH-. In particular, a group having a structure in which the methylene group at the sulfur atom-side terminal of an alkyl group having 1 to 40 carbon atoms is substituted with -CO-O-, that is, -CO-O-R "(R" is substituted. The group represented by an alkyl group having 1 to 39 carbon atoms which may have a group) or the methylene group at the sulfur atom side terminal of an arylalkyl group having 6 to 35 carbon atoms is -CO-NH-. The group of the structure substituted with, that is, -CO-NH-R'''(R''' may have a substituent, is an aryl group having 6 to 34 carbon atoms or 6 to 34 carbon atoms. It is preferable that it is a group represented by (arylalkyl group), and in particular, it is preferably a group represented by −CO—OR ″.

In the present invention, the R ″ is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, and among them, 1 carbon atom which may have a substituent. It is preferably an alkyl group of ~ 8, particularly preferably an unsubstituted alkyl group having 1 to 8 carbon atoms, and particularly preferably an unsubstituted alkyl group having 3 to 6 carbon atoms. Is preferable, and in particular, iso-propyl, n-butyl, sec-butyl, tert-butyl, iso-butyl, n-pentyl, iso-pentyl, and tert-pentyl are preferable, and among them, n- It is preferable that butyl, sec-butyl, tert-butyl, iso-butyl, tert-butyl, that is, R ¹ is a group represented by -CO-OC ₄ H ₉ , and particularly R ″. Is tert-butyl, that is, R ¹ is preferably a -CO-O-tert-butyl group.
Further, the R'''is preferably an arylalkyl group having 6 to 12 carbon atoms. By the R '' and R '''is a group of the above, the compound A is that the elimination control of R ¹ is facilitated.

The above n is an integer of 2 or more and 10 or less, but is preferably 3 or more and 8 or less from the viewpoint of obtaining a compound capable of forming a composition excellent in patterning accuracy and heat resistance. It is preferably 4 or more and 7 or less, and particularly preferably 4 or more and 6 or less. This is because when the above n is in the above range, the above compound A can obtain a composition having more excellent heat resistance.
In the present invention, it is easy to form a composition which is excellent in patterning accuracy and heat resistance, has an excellent balance of cross-linking density and hydrophobicity, and can stably form a patterned cured product against variations in alkali development time. From the viewpoint of becoming, it is preferable that the above n is 5 or more and 6 or less.

Said X is is used as a linking group that links the n -SR ^1.
An aliphatic group having 1 to 40 carbon atoms having the same number of valences as n, an aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, and a heterocycle having 2 to 35 carbon atoms represented by X above. The containing groups are an aliphatic group having 1 to 40 monovalent carbon atoms, an aromatic hydrocarbon ring-containing group having 6 to 35 monovalent carbon atoms, and a complex having 2 to 35 monovalent carbon atoms, respectively. It is a group having a structure in which n-1 hydrogen atoms are removed from the ring-containing group.
Examples of the above-mentioned aliphatic group having 1 to 40 monovalent carbon atoms, aromatic hydrocarbon ring-containing group having 6 to 35 monovalent carbon atoms, and heterocyclic ring-containing group having 2 to 35 monovalent carbon atoms include An aliphatic group having a monovalent carbon atom number of 1 to 40 represented by R ¹ , an aromatic hydrocarbon ring-containing group having a monovalent carbon atom number of 6 to 35, and a complex having a monovalent carbon atom number of 2 to 35. Examples thereof include groups similar to ring-containing groups.
One or more of the methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group and heterocyclic ring-containing group in X is −O−, −S−, −CO−, −O—CO−,. -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH It may be replaced with a group selected from -CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -SS- or -SO _{2-, or oxygen.} It may be replaced with a group in which these groups are combined under the condition that the atoms are not adjacent to each other.
That is, in X, one or more of the methylene groups in the aliphatic group, the aromatic hydrocarbon ring-containing group and the heterocyclic ring-containing group are -O-, -S-, -CO-, -O-CO. -, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, Groups selected from -NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -S-S- or -SO _2- , or oxygen atoms are not adjacent It may be a group having a structure in which these groups are conditionally replaced with a group that combines these groups.
The R'represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and as the alkyl group having 1 to 8 carbon atoms, a predetermined number of carbon atoms among the alkyl groups represented by ^{R 1 is used.} There are things that meet.

Examples of the divalent aliphatic group represented by X having 1 to 40 carbon atoms include a group having a structure in which one hydrogen atom is removed from the monovalent aliphatic group having 1 to 40 carbon atoms. , For example, alkylenes such as methylene, ethylene, propylene, butylene, butyldiyl; groups in which the methylene chain of the above alkylene is replaced with -O-, -S-, -CO-O-, -O-CO-; ethanediol, A group containing a residue of a polyol such as propanediol, butanediol, pentanediol, or hexanediol (for example, a group represented by the general formula (X1) described later); ethanedithiol, propanedithiol, butanedithiol, pentanedithiol, hexane. Examples thereof include residues of dithiol such as dithiol and groups in which these groups are substituted with substituents described later.
Examples of the trivalent aliphatic group represented by X having 1 to 40 carbon atoms include a group having a structure in which two hydrogen atoms are removed from the monovalent aliphatic group having 1 to 40 carbon atoms. , For example, an alkylidine such as propyridine, 1,1,3-butylidine; a group containing a residue of a polyol such as trimethylolpropane (for example, a group represented by the general formula (X2) described later) and a group thereof. Examples thereof include groups substituted with substituents described later.
Examples of the tetravalent aliphatic group represented by X having 1 to 40 carbon atoms include a group having a structure in which three hydrogen atoms are removed from the monovalent aliphatic group having 1 to 40 carbon atoms. For example, a group containing a residue of a polyol such as pentaerythritol (for example, a group represented by the general formula (X3) described later) and a group in which these groups are substituted with a substituent described later can be mentioned.
Examples of the hexavalent aliphatic group having 1 to 40 carbon atoms represented by X include a group having a structure in which 5 hydrogen atoms are removed from the monovalent aliphatic group having 1 to 40 carbon atoms. For example, a group containing a residue of a polyol such as dipentaerythritol (for example, a group represented by the general formula (X4) described later) and a group in which these groups are substituted with a substituent described later can be mentioned.

The aromatic hydrocarbon ring-containing group having a divalent carbon atom number of 6 to 35 represented by X includes one hydrogen atom from the aromatic hydrocarbon ring-containing group having a monovalent carbon atom number of 6 to 35. Groups of the excluded structure include, for example, areylene groups such as phenylene and naphthylene; residues of bifunctional phenols such as catechol and bisphenol; 2,4,8,10-tetraoxaspiro [5,5] undecane and the like. Examples thereof include groups in which these groups are substituted with substituents described later.
The aromatic hydrocarbon ring-containing group having a trivalent carbon atom number of 6 to 35 represented by X includes two hydrogen atoms from the aromatic hydrocarbon ring-containing group having a monovalent carbon atom number of 6 to 35. Examples of the groups having the removed structure include phenyl-1,3,5-trimethylene and groups in which these groups are substituted with substituents described later.

As the heterocyclic group having a divalent carbon atom number of 2 to 35 represented by X, a group having a structure obtained by removing one hydrogen atom from the heterocyclic ring-containing group having a monovalent carbon atom number to 2 to 35 is used. Examples thereof include a group having a pyridine ring, a pyrimidine ring, a piperidine ring, a piperazine ring, a triazine ring, a furan ring, a thiophene ring, an indole ring and the like, and substitution in which one or more of hydrogen atoms of these groups are described later. Examples include groups substituted with groups.
As the heterocyclic group having a trivalent carbon atom number of 2 to 35 represented by X, a group having a structure obtained by removing two hydrogen atoms from the heterocyclic ring-containing group having a monovalent carbon atom number to 2 to 35 is used. Examples thereof include a group having an isocyanul ring (for example, a group having a structure represented by the general formula (X5) described later), a group having a triazine ring, and one or more hydrogen atoms of these groups. Examples thereof include groups substituted with substituents described later.
As the heterocyclic group having a tetravalent carbon atom number of 2 to 35 represented by X, a group having a structure obtained by removing three hydrogen atoms from the heterocyclic ring-containing group having a monovalent carbon atom number of 2 to 35 is used. Examples thereof include a group having a glycoluril group (for example, a structure represented by the general formula (X6) described later) and a group in which a hydrogen atom of this group is substituted with a substituent described later.

Each functional group such as an aliphatic group, an aromatic hydrocarbon ring-containing group and a heterocyclic ring-containing group in X may have a substituent, and unless otherwise specified, each functional group has a substituent. It is an unsubstituted functional group or a functional group having a substituent.
Such aliphatic group, an aromatic hydrocarbon ring-containing group, the one or substituents replacing two or more hydrogen atoms of each functional group such as a heterocyclic ring-containing group, an aliphatic group in the above R ¹ The content can be the same as that of the substituent that replaces the hydrogen atom of.

In the present invention, from the viewpoint of obtaining a compound capable of forming a composition excellent in patterning accuracy and heat resistance, the above X is an aliphatic group having 1 to 40 carbon atoms or 2 to 35 carbon atoms. It is preferably a heterocyclic group, particularly an aliphatic group having 10 to 40 carbon atoms and a heterocyclic group having 5 to 25 carbon atoms, and particularly preferably having 15 to 30 carbon atoms. It is preferably an aliphatic group or a heterocycle-containing group having 10 to 20 carbon atoms, and more particularly, an aliphatic group having 25 to 30 carbon atoms or a heterocyclic ring-containing group having 11 to 15 carbon atoms. Is preferable. This is because when the above-mentioned X is the above-mentioned group, a compound capable of forming a composition excellent in patterning accuracy and heat resistance can be obtained.

In the present invention, from the viewpoint of easy synthesis of compound A, the aliphatic group having 1 to 40 carbon atoms, the aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, and the carbon atom number 2 to 35 in X are described above. One or more of the methylene groups in the heterocyclic group of -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -O It may be replaced with a group selected from -CO-NH-, -NR'-, -S-S- or -SO _2- , or these groups may be combined under the condition that the oxygen atoms are not adjacent to each other. It is preferable that one or two or more methylene groups are replaced with —O—CO−, −CO—O−, and in particular, n groups are replaced. It is preferable that the methylene group is replaced with -O-CO-, -CO-O-.
That is, X is one of an aliphatic group having 1 to 40 carbon atoms, an aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, and a methylene group in a heterocyclic ring-containing group having 2 to 35 carbon atoms. Or two or more are -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-,- It is preferable that the group is a group selected from SS- or -SO _2- , or a group having a structure in which the oxygen atoms are replaced with a group in which these groups are combined under the condition that the oxygen atoms are not adjacent to each other. It is preferable that one or more are groups having a structure substituted with -O-CO- or -CO-O-, and in particular, n methylene groups are -O-CO- or -CO-. It is preferably a group replaced with O−.

In the present invention, the aliphatic group having 1 to 40 carbon atoms represented by X is a group having a polyol residue (for example, a group represented by the following general formulas (X1) to (X4)). It is preferable to have.
Further, the heterocyclic group having 2 to 35 carbon atoms represented by X is represented by an isocyanul ring (structure represented by the following general formula (X5)) or a glycoluril group (represented by the following general formula (X6)). It is preferable that the group has a structure (s).
This is because when the above-mentioned X is the above-mentioned group, a compound capable of forming a composition excellent in patterning accuracy and heat resistance can be obtained. Further, the compound A can be easily synthesized.
The hydrogen atom in the structure represented by the general formulas (X1) to (X6) may be substituted with a substituent. The substituent replacing the hydrogen atom, may be similar to those in the substituents replacing a hydrogen atom of an aliphatic group in the above R ^1.

（式中、ａ１は、１〜２０の整数であり、＊は、結合箇所を表す。）

(In the formula, a1 is an integer of 1 to 20, and * represents a joint location.)

The a1 is an integer of 1 to 20, preferably an integer of 2 to 10, and more preferably an integer of 3 to 5.

More specifically, as the compound A, compounds represented by the following general formulas (A1) to (A6) can be preferably used.
In the present invention, the compound A is preferably a compound represented by the following general formula (A4) or (A6). This is because, since the compound A is a compound having the above structure, it becomes a compound capable of forming a composition excellent in patterning accuracy and heat resistance, and in particular, a composition excellent in heat resistance can be formed.
In the present invention, the compound A is preferably a compound represented by the following general formula (A4). This is because the patterning accuracy and the heat resistance are improved as well as the development margin, and as a result, the patterning accuracy is particularly excellent.

The reason why the compounds represented by the general formulas (A4) and (A6) are excellent in both patterning accuracy and heat resistance and can form a composition having excellent heat resistance in particular is explained. , Is inferred as follows.
The compound represented by the general formula (A4) has as many as 6 thiol groups generated after the removal of the protecting group, and the thiol groups are arranged so as to extend in all directions. Therefore, by including the compound A, a region having a high crosslink density can be formed around the compound A. As a result, the heat resistance is excellent.
Further, the structure represented by (X4) contained in the six protected thiol groups or the sites to which the thiol groups are bonded contained in the compound represented by the above general formula (A4) has a relatively large molecular weight and is central. By having a structure that spreads in 6 directions from the oxygen atom of the above, there is little curing shrinkage due to cross-linking. Therefore, it becomes easy to reduce the shrinkage during the heat treatment. Therefore, the compound represented by the above general formula (A4) can have an excellent balance between patterning accuracy and heat resistance, and can easily exhibit particularly excellent heat resistance. ..
Further, the compound represented by the general formula (A4) has a structure that spreads in six directions and has a large molecular weight, so that the diffusion rate in the composition is low. Therefore, even if the protecting group is eliminated from some compounds, the cross-linking between the polymerizable components is unlikely to proceed. As a result, the patterning accuracy is improved.
Further, the structure represented by (X4) contained in the six protected thiol groups or the site to which the thiol group is bonded tends to have a relatively large molecular weight and a highly hydrophobic site. Therefore, the compound represented by the general formula (A4) facilitates the formation of a cured product having excellent resistance to an alkaline developer, and the composition containing the compound has an excellent development margin.
As described above, the compound represented by the above general formula (A4) has excellent patterning accuracy exhibited in the polymerization step, excellent development margin exhibited in the developing step, and improvement in patterning accuracy obtained as a result. In addition, the excellent heat resistance and the like exhibited in the heat treatment process such as the subsequent post-baking process can be effectively exhibited in each step of the patterning process.
Therefore, the compound represented by the general formula (A4) is particularly suitable for, for example, a curable composition for forming a patterned cured product.
In addition, the compound represented by the general formula (A6) has a large number of thiol groups generated after elimination of the protecting group, which is four, and the thiol groups are arranged so as to extend in all directions and are rigid glycoluril. Has a group. Therefore, by including the compound A, a region having a high crosslink density can be formed around the compound A. As a result, the heat resistance is excellent.
Further, the glycoluril group contained in the compound represented by the above general formula (A6) has a rigid structure, so that the curing shrinkage due to cross-linking is small. That is, it becomes easy to reduce the shrinkage during the heat treatment. Therefore, the compound represented by the above general formula (A4) can have an excellent balance between patterning accuracy and heat resistance, and can easily exhibit particularly excellent heat resistance. ..
Further, since the compound represented by the above general formula (A6) has a rigid glycoluril group and has a bulky structure, the diffusion rate in the composition is low. Therefore, even if the protecting group is eliminated from some compounds, the cross-linking between the polymerizable components is unlikely to proceed. As a result, the patterning accuracy is improved.

（式中、Ｒ^１１及びＲ^１２は、それぞれ独立に、下記一般式（１０１）を表し、
Ｌ^１１及びＬ^１２は、炭素原子数１〜１０のアルキレン基を表し、
ａ１は、１〜２０の整数を表し、
Ｒ^２１、Ｒ^２２及びＲ^２３は、それぞれ独立に、下記一般式（１０１）又は（１０２）を表し、
Ｒ^２１、Ｒ^２２及びＲ^２３のうち、いずれか２つ以上が、下記一般式（１０１）であり、
Ｌ^２１、Ｌ^２２及びＬ^２３は、炭素原子数１〜１０のアルキレン基を表し、
Ｒ^２４は、水素原子又は一価の炭素原子数１〜４０の脂肪族基を表し、
Ｒ^３１、Ｒ^３２、Ｒ^３３及びＲ^３４は、それぞれ独立に、下記一般式（１０１）又は（１０２）を表し、
Ｒ^３１、Ｒ^３２、Ｒ^３３及びＲ^３４のうち、いずれか２つ以上が、下記一般式（１０１）であり、
Ｌ^３１、Ｌ^３２、Ｌ^３３及びＬ^３４は、炭素原子数１〜１０のアルキレン基を表し、
Ｒ^４１、Ｒ^４２、Ｒ^４３、Ｒ^４４、Ｒ^４５及びＲ^４６は、それぞれ独立に、下記一般式（１０１）又は（１０２）を表し、
Ｒ^４１、Ｒ^４２、Ｒ^４３、Ｒ^４４、Ｒ^４５及びＲ^４６のうち、いずれか２つ以上が、下記一般式（１０１）であり、
Ｌ^４１、Ｌ^４２、Ｌ^４３、Ｌ^４４、Ｌ^４５及びＬ^４６は、炭素原子数１〜１０のアルキレン基を表し、
Ｒ^５１、Ｒ^５２及びＲ^５３は、それぞれ独立に、下記一般式（１０１）又は（１０２）を表し、
Ｒ^５１、Ｒ^５２及びＲ^５３のうち、いずれか２つ以上が、下記一般式（１０１）であり、
Ｌ^５１、Ｌ^５２及びＬ^５３は、炭素原子数１〜１０のアルキレン基を表し、
Ｒ^６１、Ｒ^６２、Ｒ^６３及びＲ^６４は、それぞれ独立に、下記一般式（１０１）又は（１０２）を表し、
Ｒ^６１、Ｒ^６２、Ｒ^６３及びＲ^６４のうち、いずれか２つ以上が、下記一般式（１０１）であり、
Ｌ^６１、Ｌ^６２、Ｌ^６３及びＬ^６４は、炭素原子数１〜１０のアルキレン基を表し、
Ｒ^６５及びＲ^６６は、それぞれ独立に、水素原子又は一価の炭素原子数１〜４０の脂肪族基を表し、
前記脂肪族基中のメチレン基の１つ又は２つ以上は、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｏ−、−Ｓ−ＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｓ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＮＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＮＨ−、−ＮＲ’−、−Ｓ−Ｓ−若しくは−ＳＯ_２−から選ばれた基で置き換えられている場合があるか、又は酸素原子が隣り合わない条件でこれらの基を組み合わせた基で置き換えられている場合がある。）

(In the formula, R ¹¹ and R ¹² independently represent the following general formula (101).
L ¹¹ and L ¹² represent an alkylene group having 1 to 10 carbon atoms.
a1 represents an integer of 1 to 20 and represents
R ²¹ , R ²² and R ²³ independently represent the following general formula (101) or (102), respectively.
Any two or more of R ²¹ , R ²² and R ²³ have the following general formula (101).
L ²¹ , L ²² and L ²³ represent an alkylene group having 1 to 10 carbon atoms.
R ²⁴ represents an aliphatic group having a hydrogen atom or a monovalent carbon atom number of 1 to 40.
R ³¹ , R ³² , R ³³ and R ³⁴ independently represent the following general formula (101) or (102).
Any two or more of R ³¹ , R ³² , R ^33, and R ³⁴ have the following general formula (101).
L ³¹ , L ³² , L ³³ and L ³⁴ represent an alkylene group having 1 to 10 carbon atoms.
R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ independently represent the following general formula (101) or (102), respectively.
Any two or more of R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ is the following general formula (101).
L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ and L ⁴⁶ represent an alkylene group having 1 to 10 carbon atoms.
R ⁵¹ , R ⁵² and R ⁵³ independently represent the following general formula (101) or (102), respectively.
Any two or more of R ⁵¹ , R ^52, and R ⁵³ have the following general formula (101).
L ⁵¹ , L ⁵² and L ⁵³ represent an alkylene group having 1 to 10 carbon atoms.
R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ independently represent the following general formula (101) or (102).
Any two or more of R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ is the following general formula (101).
L ⁶¹ , L ⁶² , L ⁶³ and L ⁶⁴ represent an alkylene group having 1 to 10 carbon atoms.
R ⁶⁵ and R ⁶⁶ each independently represent a hydrogen atom or an aliphatic group having 1 to 40 monovalent carbon atoms.
One or more of the methylene groups in the aliphatic group are -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-,-. S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -O- It may have been replaced with a group selected from CO-NH-, -NR'-, -S-S- or -SO _2- , or these groups were combined under the condition that the oxygen atoms were not adjacent to each other. May have been replaced by a group. )

（式中、Ｒ^１は、一価の炭素原子数１〜４０の脂肪族基、一価の炭素原子数６〜３５の芳香族炭化水素環含有基、一価の炭素原子数２〜３５の複素環含有基又は一価の炭素原子数０〜４０のシリル基を表し、
＊は、結合箇所を表し、
前記脂肪族基、芳香族炭化水素環含有基、複素環含有基及びシリル基中のメチレン基の１つ又は２つ以上は、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｏ−、−Ｓ−ＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｓ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＮＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＮＨ−、−ＮＲ’−、−Ｓ−Ｓ−若しくは−ＳＯ_２−から選ばれた基で置き換えられている場合があるか、又は酸素原子が隣り合わない条件でこれらの基を組み合わせた基で置き換えられている場合がある。）

(In the formula, R ¹ is an aliphatic group having a monovalent carbon atom number of 1 to 40, an aromatic hydrocarbon ring-containing group having a monovalent carbon atom number of 6 to 35, and a monovalent carbon atom number of 2 to 35. Represents a heterocyclic group or a silyl group having a monovalent carbon number of 0 to 40.
* Indicates the joint location
One or more of the methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocyclic group and silyl group are -O-, -S-, -CO- and -O-CO-. , -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-,- Is it sometimes replaced with a group selected from NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -S-S- or -SO _2-? , Or the oxygen atoms may be replaced with a combined group of these groups under the condition that they are not adjacent to each other. )

The monovalent aliphatic group having 1 to 40 monovalent carbon atoms represented by ^{R 24} in the general formula (A2) and R ^{65 and R 66} in (A6) is the monovalent group used in the ^{above R 1.} Examples thereof include aliphatic groups having 1 to 40 carbon atoms.
^{R 1} in the general formula (101) is the same ^{as R 1} in the general formula (A).

L ^11, L ¹² , L ²¹ , L ²² , L ²³ , L ³¹ , L ³² , L ³³ , L ³⁴ , L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ , L ⁴⁶ , L ⁵¹ , L ^{The alkylene group having 1 to 10 carbon atoms represented by 52} , L ⁵³ , L ⁶¹ , L ⁶² , L ⁶³ and L ⁶⁴ has a structure in which one hydrogen atom is removed from the alkyl group having 1 to 10 carbon atoms. The divalent group of.
As the alkyl group having 1 to 10 carbon atoms, for example, ^one of the alkyl groups having 1 to 40 carbon atoms in R 1 having a predetermined carbon atom number can be used.
More specific examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, propylene, butylene, and butyldiyl.
Further, the alkylene group having 1 to 10 carbon atoms may be linear or branched. Examples of the linear group include a propylene group in which a hydrogen atom is removed from the 1st and 2nd positions of propane as a group having 3 carbon atoms, and a hydrogen atom is removed from the 1st and 3rd positions of propane. Can be mentioned as a trimethylene group.

^{As for R 21} , R ²² and R ²³ in the general formula (A2), two or more of them may be the general formula (101), but it is preferable that all of them are the general formula (101). ..
^{As for R 31} , R ³² , R ³³ and R ³⁴ in the general formula (A3), two or more of them may be the general formula (101), but three or more are the general formula (101). It is preferable that all of them have the above general formula (101).
^{Two or more of R 41} , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ in the general formula (A4) may be the general formula (101), but R ⁴¹ , R ⁴² , It is preferable that four or more of R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ have the above general formula (101), and among them, R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ^46. It is preferable that all of the above formulas (101).
^{Two or more of R 51} , R ⁵² and R ⁵³ in the general formula (A5) may be the general formula (101), but all of R ⁵¹ , R ⁵² and R ⁵³ are the general formula (A5). The formula (101) is preferable.
^{Two or more of R 61} , R ⁶² , R ⁶³ and R ⁶⁴ in the general formula (A6) may be the general formula (101), but of R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ . It is preferable that three or more are of the above general formula (101), and it is preferable that all of R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are of the above general formula (101).
R ²¹ , R ²² and R ²³ , R ³¹ , R ³² , R ³³ and R ³⁴ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , R ⁵¹ , R ⁵² and R ⁵³ , R ^{This is because, when 61} , R ⁶² , R ⁶³ and R ⁶⁴ are the above-mentioned groups, the compound A can form a composition excellent in patterning accuracy and heat resistance.

^{The preferred structure for R 1} in the general formula (101) is the same as the preferred structure ^{for R 1} in the general formula (A).

In the present invention, the R ²⁴ is preferably an aliphatic group having 1 to 40 carbon atoms, particularly preferably an alkyl group having 1 to 20 carbon atoms, and above all, an alkyl group having 1 to 20 carbon atoms. Alkyl groups having 1 to 10 are preferable, and alkyl groups having 1 to 5 carbon atoms are particularly preferable, and alkyls having 1 to 3 carbon atoms such as methyl, ethyl, n-propyl, and iso-propyl are preferable. It is preferably a group. This is because when the R ²⁴ is the above-mentioned group, the compound A can form a composition excellent in patterning accuracy and heat resistance.
In the present invention, the R ⁶⁵ and R ⁶⁶ are preferably hydrogen atoms or alkyl groups having 1 to 20 carbon atoms, and among them, hydrogen atoms or alkyl groups having 1 to 10 carbon atoms. It is preferable, and in particular, it is preferably a hydrogen atom. This ^{is because, when R 65} and R ⁶⁶ are the above-mentioned groups, the above-mentioned compound A can form a composition excellent in patterning accuracy and heat resistance.

A1 in the general formula (A1) is the same as a1 in the general formula (X1).

The L ¹¹ and L ¹² are preferably alkylene groups having 1 to 5 carbon atoms, and among them, linear alkylene groups having 1 to 3 carbon atoms or branched alkylene groups having 3 to 5 carbon atoms. Is preferable.
The above L ¹¹ and L ¹² may be the same group or different groups, respectively, but from the viewpoint of easy synthesis, they are preferably the same group.
The L ²¹ , L ²² and L ²³ are preferably alkylene groups having 1 to 5 carbon atoms, and among them, linear alkylene groups having 1 to 3 carbon atoms or branched alkylene groups having 3 to 5 carbon atoms. It is preferably a group.
The above L ²¹ , L ²² and L ²³ may be the same group or different groups, respectively, but from the viewpoint of easy synthesis, they are preferably the same group.
The L ³¹ , L ³² , L ³³ and L ³⁴ are preferably alkylene groups having 1 to 5 carbon atoms, and among them, linear alkylene groups having 1 to 3 carbon atoms or branched 3 to 3 to It is preferably an alkylene group of 5.
The above L ³¹ , L ³² , L ³³ and L ³⁴ may be the same group or different groups, respectively, but from the viewpoint of easy synthesis, they are preferably the same group.
The L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ and L ⁴⁶ are preferably alkylene groups having 1 to 5 carbon atoms, and among them, linear alkylene groups having 1 to 3 carbon atoms. It is preferably a group or a branched 3-5 alkylene group.
The above L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ and L ⁴⁶ may be the same group or different groups, respectively, but from the viewpoint of easy synthesis, they are the same group. Is preferable.
The L ⁵¹ , L ⁵² and L ⁵³ are preferably alkylene groups having 1 to 5 carbon atoms, and among them, linear alkylene groups having 1 to 3 carbon atoms or branched alkylene groups having 3 to 5 carbon atoms. It is preferably a group.
The above L ⁵¹ , L ⁵² and L ⁵³ may be the same group or different groups, respectively, but from the viewpoint of easy synthesis, the same group is preferable.
The L ⁶¹ , L ⁶² , L ⁶³ and L ⁶⁴ are preferably alkylene groups having 1 to 5 carbon atoms, and among them, linear alkylene groups having 1 to 3 carbon atoms or branched 3 to 3 to It is preferably an alkylene group of 5.
The above L ⁶¹ , L ⁶² , L ⁶³ and L ⁶⁴ may be the same group or different groups, respectively, but from the viewpoint of easy synthesis, they are preferably the same group.
L ^11, L ¹² , L ²¹ , L ²² , L ²³ , L ³¹ , L ³² , L ³³ , L ³⁴ , L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ , L ⁴⁶ , L ⁵¹ , L ^{This is because 52} , L ⁵³ , L ⁶¹ , L ⁶² , L ⁶³ and L ⁶⁴ are in the above range, so that the compound can form a composition excellent in patterning accuracy and heat resistance.
L ^11, L ¹² , L ²¹ , L ²² , L ²³ , L ³¹ , L ³² , L ³³ , L ³⁴ , L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ , L ⁴⁶ , L ⁵¹ , L Specific examples of the linear alkylene group having 1 to 3 carbon atoms represented by ⁵² , L ⁵³ , L ⁶¹ , L ⁶² , L ⁶³ and L ^{64 include methylene and ethylene (ethane-1,2).} -Diyl), propylene (propane-1,3-diyl) and the like.
L ^11, L ¹² , L ²¹ , L ²² , L ²³ , L ³¹ , L ³² , L ³³ , L ³⁴ , L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ , L ⁴⁶ , L ⁵¹ , L Specific examples of the branched 3 to 5 alkylene groups represented by ⁵² , L ⁵³ , L ⁶¹ , L ⁶² , L ⁶³ and L ^{64 are propane-1,1-diyl and propane-1,2.} -Zyle, Butane-1,1-Gyle, Butane-1,2-Gyle, Butane-1,3-Gyle, Pentane-1,1-Gyle, Pentane-1,2-Gyle, Pentane-1,3-Gyle , Pentane-1,4-Zyle and the like.

The number of thiol groups in the compound A (SH group), namely, in the compound A, as the number of thiol groups not protected by a protecting group R ^1, can form a good composition by the patterning accuracy and heat resistance Anything can be used, and the smaller the number, the more preferable.
The number of the thiol groups is preferably 2 or less, preferably 1 or less, and 0 in the compound A, that is, the compound A does not contain a thiol group. preferable. This is because it is possible to form an excellent composition due to patterning accuracy and heat resistance.

The molecular weight of the compound A may be any as long as it can form a composition excellent in patterning accuracy and heat resistance. For example, it is preferably 3000 or less, and more preferably 300 or more and 2500 or less. In particular, it is preferably 500 or more and 2000 or less, and particularly preferably 600 or more and 1800 or less.
Further, the molecular weight of the compound A is 1000 from the viewpoint that the patterning accuracy and the heat resistance are excellent and the composition containing the compound is excellent in the development margin, particularly from the viewpoint of exhibiting the excellent heat resistance. It is preferably 1700 or more, more preferably 1200 or more and 1600 or less, and particularly preferably 1300 or more and 1500 or less.
The molecular weight of the compound after desorption of the protecting group R ¹ of the compound A, that is, the molecular weight of the ^{thiol compound in which the −SH group is not protected by the protecting group R 1} , is excellent in patterning accuracy and heat resistance, and contains the above compound. From the viewpoint that the composition has an excellent development margin, particularly from the viewpoint of exhibiting excellent heat resistance, it is preferably 400 or more and 1000 or less, more preferably 500 or more and 900 or less, and particularly particularly. It is preferably 600 or more and 800 or less.

The equivalent amount of the protected thiol group (SR ¹ ) in the compound A, that is, the value obtained by dividing the molecular weight of the compound A by the number of the ^{protected thiol groups (SR 1} ) (molecular weight of the compound A / number of the ^{protected thiol groups SR 1)} , 500 or less, particularly preferably 100 or more and 400 or less, and particularly preferably 150 or more and 300 or less. This is because when the protected thiol group equivalent of the compound A is within the above range, the compound can form a composition having excellent patterning accuracy and heat resistance.
The protective thiol group (SR ¹ ) equivalent in the compound A is excellent in patterning accuracy and heat resistance, and exhibits particularly excellent heat resistance from the viewpoint that the composition containing the compound has an excellent development margin. From the viewpoint of the above, it is preferably 200 or more and 270 or less, particularly preferably 220 or more and 260 or less, and particularly preferably 230 or more and 250 or less.
Thiol group equivalent of the compound A compound after removal of the protecting groups R ^1, i.e., -SH group is not protected by a protecting group R ^1, with a thiol group equivalent of the thiol compound is excellent in patterning accuracy and heat resistance From the viewpoint that the composition containing the above compound has an excellent development margin, particularly from the viewpoint of exhibiting excellent heat resistance, it is preferably 400 or more and 1000 or less, and 500 or more and 900 or less. It is preferably 600 or more and 800 or less.

The compound A can be protected group R ¹ by heating shall desorption.
The temperature at which the protective group R ¹ contained in the compound A is released, for example, be a 100 ° C. or higher 300 ° C. or less, among others, preferably at 120 ° C. or higher 250 ° C. or less, 0.99 ° C. or higher It is preferably 230 ° C. or lower.
The desorption temperature can be a temperature showing a heat loss of 5% by weight by differential thermal analysis.
As a measuring method, for example, using STA (Differential Thermal Weight Simultaneous Measuring Device), the temperature rises at about 5 mg, nitrogen 200 mL / min atmosphere, normal pressure, temperature rise start temperature 30 ° C., temperature rise end temperature 500 ° C., rise. The thermogravimetric weight loss of the sample when the temperature is raised at a temperature rate of 10 ° C./min can be measured, and the temperature at the time when the weight is reduced by 5% with respect to the sample weight at 30 ° C. can be set as the 5% weight loss temperature.
As the differential thermogravimetric simultaneous measurement device, STA7000 (manufactured by Hitachi High-Tech Science) can be used.

Specific examples of the compound A include the compounds represented by the following.

The method for producing the compound A is not particularly limited as long as it can obtain a desired structure. The above-mentioned production method is described in, for example, JP-A-2015-05909, a method for forming an esterified compound of a hydroxy group of a polyol and an SH group-containing carboxylic acid, as described in JP-A-2017-031318. As described above, the thiol group-containing compound is prepared by a known method such as a method of adding thioacetic acid to an ethylenically unsaturated group of a compound having an ethylenically unsaturated group and then reducing the compound with a boron hydride compound. Examples thereof include a method of producing and then reacting a thiol group-containing compound with an acid anhydride, a acid compound, a Bocification reagent, an alkyl halide compound, a silyl chloride compound, an allyl ether compound and the like.

The compound A can be used as a thiol generator that generates SH groups by heat treatment or the like, and for example, a thiol added to a composition such as a curable composition containing a polymerizable component B such as a radically polymerizable component. It can be used as a generator.
The curable composition is used as a heat-curable paint, a photo-curable paint or varnish, a heat-curable adhesive, a photo-curable adhesive, a printed substrate, or a color television, a PC monitor, a mobile information terminal, or a digital camera. Color filters in liquid crystal display panels for color display, color filters for CCD image sensors, photo spacers, black column spacers, electrode materials for plasma display panels, touch panels, touch sensors, powder coatings, printing inks, printing plates, adhesives, etc. , Dental compositions, photoengraving resins, gel coats, electronic engineering photo resists, electroplating resists, etching resists, both liquid and dry films, solder resists, and color filters for various display applications. Alternatively, a plasma display panel, an electroluminescent display device, and a resist for forming a structure in the manufacturing process of an LCD, a composition for encapsulating electric and electronic parts, a solder resist, a magnetic recording material, a micromechanical part, a waveguide, etc. Optical switch, plating mask, etching mask, color test system, glass fiber cable coating, screen printing stencil, material for manufacturing three-dimensional objects by stereolithography, holography recording material, image recording material, microelectronic circuit , Decolorizing material, Decolorizing material for image recording material, Decolorizing material for image recording material using microcapsules, Photoresist material for printed wiring board, Photoresist material for UV and visible laser direct imaging system, Printed circuit board It can be used for various purposes such as a photoresist material used for forming a dielectric layer in the sequential lamination of the above, a photoresist material for 3D mounting, a protective film, and the like, and the application is not particularly limited.
Further, the curable composition containing the compound A is preferably used for forming a patterned cured product having excellent both patterning accuracy and heat resistance, and in particular, it is patterned by a photolithography method and patterned cured. It is preferably used in a photocurable composition used for forming a substance.
More specifically, the curable composition is preferably used for color filters, photospacers, black column spacers, electrode materials, photoresists, solder resists, overcoats, insulating films, black matrices, partition materials and the like. be able to.
In the present invention, when the compound A is used in a photocurable composition, it is used in a photocurable composition for forming a patterned cured product having a width of 200 μm or less, that is, for forming a pattern having a width of 200 μm or less. It is preferable to be used in the photocurable composition of the above, and among them, it is preferably used in the photocurable composition for pattern formation of 0.1 μm or more and 150 μm or less, and in particular, pattern formation of 0.5 μm or more and 100 μm or less. It is preferable to use it in a photocurable composition for pattern formation, and it is preferable to use it in a photocurable composition for pattern formation of 1 μm or more and 50 μm or less. Since it is used for pattern formation with the above width, the effect of excellent patterning accuracy and heat resistance of the compound A and the effect of facilitating the formation of a patterned cured product having a narrow line width can be more effectively exhibited. Is. Further, it is possible to stably form a pattern having a high aspect ratio.
When the compound A is used in a photocurable composition for pattern formation, the film thickness of the pattern is preferably 0.1 μm or more and 100 μm or less, and preferably 0.3 μm or more and 50 μm or less. , 0.5 μm or more and preferably 10 μm or less, and preferably 1 μm or more and 5 μm or less. When the film thickness is within the above range, the effect of excellent patterning accuracy and heat resistance of the compound A can be more effectively exhibited, and a pattern having a high aspect ratio can be stably formed. be.

B. Thiol generator Next, the thiol generator of the present invention will be described.
The thiol generator of the present invention is characterized by containing the above-mentioned compound (the above-mentioned compound A).

According to the present invention, by containing the above compound A, it becomes a thiol generator capable of forming a composition having excellent patterning accuracy and heat resistance.

1. 1. Compound The type of the compound A used in the thiol generator of the present invention may be any one capable of forming a composition having excellent patterning accuracy and heat resistance, and only one type may be used in the thiol generator. There may be two or more types. The thiol generator can contain, for example, two or more and five or less compounds A.

The content of the compound A may be any as long as it can form a composition having excellent patterning accuracy and heat resistance, and is appropriately set according to the type of thiol generator and the like.
As for the content of the compound A, for example, 100 parts by mass of the solid content of the thiol generator, that is, the thiol generator can be the compound A.
Further, the content may be less than 100 parts by mass in 100 parts by mass of the solid content of the thiol generator, that is, the thiol generator may be a composition containing the compound A and other components, for example, 20. It can be more than 99.99 parts by mass and less than 99.99 parts by mass.
In the present invention, from the viewpoint of facilitating the formation of a composition having excellent patterning accuracy and heat resistance, the lower limit of the content is preferably 50 parts by mass or more, and more than 70 parts by mass. It is preferably 90 parts by mass or more.
Further, from the viewpoint of facilitating the particle size control of the thiol generator, the upper limit of the content is preferably 99 parts by mass or less, and more preferably 95 parts by mass or less. In particular, it is preferably 90 parts by mass or less.
The solid content includes all components other than the solvent.
Further, the content of the compound A indicates the total amount of the compound A when two or more kinds of the compounds A are contained.

Since the above-mentioned compound A can be the same as the content described in the above-mentioned "A. compound" section, the description thereof is omitted here.

2. Other Ingredients The thiol generator may contain other ingredients other than the compound A.
Examples of such other components include "2. Polymerizable component having thiol reactivity", "3. Polymerization initiator", and "4. Polymer having a carboxyl group" of "C. Composition" described later. , "5. Other Ingredients".
The other components preferably include the polymerization initiator described in the above section "3. Polymerization initiator". This is because the composition containing the polymerizable component B can be easily produced by aggregating the components involved in the polymerization, reaction, etc. of the polymerizable component B.
The content of the radical polymerization initiator with respect to 100 parts by mass of the compound A can be the same as that described in the section “3. Polymerization initiator” of “C. Composition” described later.
The other components preferably contain a polymer that does not have the polymerizable group described in "5. Other components" from the viewpoint of facilitating the particle size control of the thiol generator. ..
The content of the other components can be appropriately set according to the use of the thiol generator, and can be, for example, 50 parts by mass or less in 100 mass by mass of the solid content of the thiol generator. It is preferably 10 parts by mass or less. This is because the thiol generator makes it easy to increase the content ratio of the compound A, and makes it easy to form a composition having excellent patterning accuracy and heat resistance.

3. 3. Production method The production method of the thiol generator may be any method as long as it can contain the compound A in a desired blending amount.
When the thiol generator contains compound A and other components, a method using a known mixing means can be mentioned.

Examples of the use of the thiol generator include applications for addition to a composition such as a curable composition containing a polymerizable component B.
The specific use and the like of the curable composition can be the same as that described in the section of "A. Compound", and thus the description thereof is omitted here.

C. Composition Next, the composition of the present invention will be described.
The composition of the present invention is characterized by having a compound represented by the following general formula (A) (Compound A) and a polymerizable component having thiol reactivity (polymerizable component B). ..

（式中、Ｒ^１は、一価の炭素原子数１〜４０の脂肪族基、一価の炭素原子数６〜３５の芳香族炭化水素環含有基、一価の炭素原子数２〜３５の複素環含有基又は一価の炭素原子数０〜４０のシリル基を表し、
Ｘは、ｎと同数の価数を有する炭素原子数１〜４０の脂肪族基、炭素原子数６〜３５の芳香族炭化水素環含有基又は炭素原子数２〜３５の複素環含有基を表し、
前記脂肪族基、芳香族炭化水素環含有基、複素環含有基及びシリル基中のメチレン基の１つ又は２つ以上は、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｏ−、−Ｓ−ＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｓ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＮＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＮＨ−、−ＮＲ’−、−Ｓ−Ｓ−若しくは−ＳＯ_２−から選ばれた基で置き換えられている場合があるか、又は酸素原子が隣り合わない条件でこれらの基を組み合わせた基で置き換えられている場合があり、
ｎは２以上１０以下の整数を表す。）

(In the formula, R ¹ is an aliphatic group having a monovalent carbon atom number of 1 to 40, an aromatic hydrocarbon ring-containing group having a monovalent carbon atom number of 6 to 35, and a monovalent carbon atom number of 2 to 35. Represents a heterocyclic group or a silyl group having a monovalent carbon number of 0 to 40.
X represents an aliphatic group having 1 to 40 carbon atoms having the same number of valences as n, an aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 35 carbon atoms. ,
One or more of the methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocyclic group and silyl group are -O-, -S-, -CO- and -O-CO-. , -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-,- Is it sometimes replaced with a group selected from NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -S-S- or -SO _2-? , Or may be replaced by a group that combines these groups under the condition that the oxygen atoms are not adjacent to each other.
n represents an integer of 2 or more and 10 or less. )

According to the present invention, since the composition contains the compound A, the composition is excellent in patterning accuracy and heat resistance.

The composition of the present invention contains the above-mentioned compound A and the polymerizable component B.
Hereinafter, each component of the composition of the present invention will be described in detail.

1. 1. Compound A
The type of the compound A may be any as long as it can form a composition having excellent patterning accuracy and heat resistance, and may be only one type in the composition or two or more types. The compound A can contain, for example, two or more and five or less compounds A.

The content of the compound A is appropriately set according to the use of the composition and the like.
Such a content can be 0.01 part by mass or more and 20 parts by mass or less, preferably 0.05 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the solid content of the composition. This is because it becomes easy to form a composition having excellent patterning accuracy and heat resistance in the composition.

Since the above-mentioned compound A can be the same as the content described in the above-mentioned "A. compound" section, the description thereof is omitted here.

2. Polymerizable component B
The polymerizable component B is not particularly limited as long as it is a compound capable of reacting with thiol and having a thiol-reactive group in which the polymerizable components can be polymerized with each other.
As such a thiol-reactive group, a radical-polymerizable group, a cationically polymerizable group and the like can be preferably used.
The polymerizable component B may contain at least one of a radically polymerizable compound having a radically polymerizable group and a cationically polymerizable compound having a cationically polymerizable group, and is a radically polymerizable component composed of a radically polymerizable compound. , A cationically polymerizable component composed of a cationically polymerizable compound, or a polymerizable component containing both a radically polymerizable compound and a cationically polymerizable compound.
Since the polymerizable component B is the above-mentioned component, for example, by using it in combination with a photopolymerization initiator such as a photoradical polymerization initiator and a photocationic polymerization initiator, the composition can be polymerized by light irradiation. This is because a patterned cured product can be formed with high patterning accuracy by the step of polymerizing the components and the step of developing.
In the present invention, the polymerizable component B preferably contains a radically polymerizable compound as the polymerizable compound B, and is particularly preferably a radically polymerizable component composed of the radically polymerizable compound. This is because the composition has an excellent curing rate because the polymerizable component B contains a radically polymerizable compound. Further, it is easy to crosslink using the compound A.

(1) Radical Polymerizable Compound The radically polymerizable compound is a compound having a radically polymerizable group.
Examples of such a radically polymerizable compound include radically polymerizable compounds described in JP-A-2016-17609.
More specific examples of the radically polymerizable group include compounds having an ethylenically unsaturated group such as an acryloyl group, a methacryloyl group, and a vinyl group.
As the radically polymerizable compound, a monofunctional compound having one radically polymerizable group and a polyfunctional compound having two or more radically polymerizable groups can be used.

As the radically polymerizable compound, a compound having an acid group and a compound having no acid group can be used.
As the acid group, it can be exemplified -COOH group, -SO ₃ H _group, -SO 2 NHCO- group, a phenolic hydroxy group, _-SO 2 NH- group, a -CO-NH-CO- group and the like.
Examples of the compound having an acid group include 4-hydroxystyrene, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, and β. -Styryl (meth) acrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, silicic acid, α-cyanosilic acid, itaconic acid, crotonic acid, propioleic acid, 4-hydroxyphenyl Examples thereof include methacrylate, 3,5-dimethyl-4-hydroxybenzylacrylamide, 4-hydroxyphenylacrylamide, 4-hydroxyphenylmaleimide, 3-maleimide propionic acid, 4-maleimide butyric acid, and 6-maleimidohexanoic acid.
Examples of the compound having an acid group include an epoxy acrylate resin in which an unsaturated monobasic acid is allowed to act on the epoxy group of the epoxy compound, and an unsaturated monobasic acid is allowed to act on the epoxy group of the epoxy compound to further increase the number of bases. Examples thereof include an acid group-containing epoxy acrylate resin such as a carboxyl group-containing epoxy acrylate resin obtained by reacting an acid anhydride.
Examples of the acid group-containing epoxy acrylate resin include Ripoxy (registered trademark) SPC-2000 and SPC-3000 manufactured by Showa Denko, Diclite (registered trademark) UE-777 manufactured by DIC, and Yupika (registered trademark) manufactured by Japan U-Pica Company. Trademark) 4015 and the like can be mentioned.
Further, as the compound having an acid group, a polymer having a methacryloyl group or an acryloyl group and a carboxyl group can also be used. As such a polymer, among the polymers described in the section of "4. Polymer having a carboxyl group" described later, a polymer having a structural unit having a methacryloyl group or an acryloyl group as a crosslinkable group is also preferable. Can be used.
As the compound having an acid group, among the polymers of the radically polymerizable compound, those having an unreacted or ex post facto added radical polymerizable group can also be used. For example, among the polymers of compounds having an acid group, the polymer having an acid group, and the polymer of a compound having no acid group, those having an unreacted or ex post facto added radical polymerizable group also have an acid group. It can be used as a compound to have.

Examples of the compound having no acid group include polymerizable styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene and p-ethylstyrene, acrylamide, acrylonitrile, vinyl-n-butyl ether and the like. Vinyl alcohol ethers, (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester , Pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropanetetraacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate and other (meth) acrylic acid esters, 2 , 2,2-Trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, maleic anhydride, maleic acid monoester, phenylmaleimide, cyclohexylmaleimide and other N-substituted maleimides Can be mentioned.

The radically polymerizable compound can be used together with a radical polymerization initiator such as a photoradical polymerization initiator and a thermal radical polymerization initiator.

(2) Cationic Polymerizable Compound The cationically polymerizable compound is a compound having a cationically polymerizable group.
Examples of such a cationically polymerizable compound include the cationically polymerizable compounds described in JP-A-2016-17609.
More specific examples of the cationically polymerizable compound include a compound having a cyclic ether group such as an epoxy compound having an epoxy group and an oxetane compound having an oxetane group, and a vinyl ether compound having a vinyl ether group.
As the cationically polymerizable compound, a monofunctional compound having one cationically polymerizable group and a polyfunctional compound having two or more cationically polymerizable groups can be used.
As the cationically polymerizable compound, a compound having an acid group and a compound having no acid group can be used.
As the cationically polymerizable compound, a polymer having an epoxy group, an oxetanyl group or a vinyl ether group, and a carboxyl group can also be used. Such a polymer is a polymer having a structural unit having an epoxy group, an oxetanyl group or a vinyl ether group as a crosslinkable group among the polymers described in the section “4. Polymer having a carboxyl group” described later. Etc. can also be preferably used.
When two or more kinds of cationically polymerizable compounds are mixed and used, they may be copolymerized in advance and used as a copolymer.
The cationically polymerizable compound can be used together with a cationic polymerization initiator such as a photocationic polymerization initiator and a thermal cationic polymerization initiator.

(3) Others The content of the above-mentioned polymerizable component B is not particularly limited as long as it can be excellent in patterning accuracy and heat resistance. For example, the solid content of the composition of the present invention. It is preferably 10 parts by mass or more and 90 parts by mass or less, particularly 20 parts by mass or more and 80 parts by mass or less, and particularly 30 parts by mass or more and 70 parts by mass or less in 100 parts by mass. Is preferable. This is because the composition is excellent in patterning accuracy and heat resistance.
The content of the polymerizable component B is not particularly limited as long as it can be excellent in patterning accuracy and heat resistance, and is, for example, the total of the compound A and the polymerizable component B. It is preferably 70 parts by mass or more, preferably 80 parts by mass or more and 99.9 parts by mass or less, and particularly preferably 90 parts by mass or more and 99 parts by mass or less in 100 parts by mass. .. This is because when the content is within the above range, the composition is excellent in patterning accuracy and heat resistance.

As the polymerizable component B, either a compound having an acid group or a compound having no acid group can be used as the polymerizable compound B, but from the viewpoint of making a composition excellent in patterning accuracy, the acid group is used. It is preferable to contain a compound having an acid group, and from the viewpoint of obtaining a composition excellent in patterning accuracy and heat resistance, it is preferable to contain both a compound having an acid group and a compound having no acid group.
More specifically, when the polymerizable component B is a radically polymerizable component, it is preferable to include a compound having an acid group as the radically polymerizable compound from the viewpoint of obtaining a composition having better patterning accuracy. From the viewpoint of obtaining a composition excellent in patterning accuracy and heat resistance, it is preferable that the radically polymerizable compound contains both a compound having an acid group and a compound having no acid group.

The content of the compound having an acid group may be one that is excellent in patterning accuracy and heat resistance, but is 1 part by mass or more and 95 parts by mass or less in 100 parts by mass of the polymerizable component B. It is preferably 1 part by mass or more and 80 parts by mass or less. This is because the composition is excellent in patterning accuracy and heat resistance.
In the present invention, from the viewpoint of making the composition more excellent in patterning accuracy, the content of the compound having an acid group is preferably 20 parts by mass or more in 100 parts by mass of the polymerizable component B. Of these, 50 parts by mass or more is preferable, and 70 parts by mass or more is particularly preferable.
From the viewpoint of making the composition more excellent in heat resistance, the content of the compound having an acid group is preferably 70 parts by mass or less in 100 parts by mass of the polymerizable component B, and above all, It is preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less.
Further, from the viewpoint of making the composition more excellent in patterning accuracy, the content of the compound having an acid group is 20 parts by mass or more in a total of 100 parts by mass of the compound A and the polymerizable component B. It is preferably 50 parts by mass or more and 90 parts by mass or less, and particularly preferably 70 parts by mass or more and 90 parts by mass or less.
From the viewpoint of making the composition more excellent in heat resistance, the content of the compound having an acid group is 80 parts by mass or less in a total of 100 parts by mass of the compound A and the polymerizable component B. Is preferable, and in particular, it is preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less.
The content of the compound having an acid group is such that when the polymerizable component B contains both a radically polymerizable compound and a cationically polymerizable compound, the radically polymerizable compound has an acid group and the cationically polymerizable compound. It shows the total content of the compounds having an acid group.

The number of functional groups of the polymerizable compound B, that is, the number of thiol-reactive groups contained in one molecule of the polymerizable compound B may be 1 or more, and is a monofunctional compound or thiol-reactive group having one thiol-reactive group. A polyfunctional compound having 2 or more of can be used.
The number of functional groups of the compound having no acid group may be 1 or more, preferably 2 or more, particularly preferably 3 or more and 8 or less, and particularly 4 or more and 7 or less. Is preferable. This is because the above composition has an excellent balance of patterning accuracy, heat resistance, and the like.
More specifically, when the polymerizable component B is a radically polymerizable component, the number of functional groups of the radically polymerizable compound having no acid group is determined from the viewpoint of the balance between patterning accuracy and heat resistance. It is preferably 2 or more, particularly preferably 3 or more and 8 or less, and particularly preferably 4 or more and 7 or less.

The polymerizable component B preferably contains a low molecular weight compound as the polymerizable compound B from the viewpoint of patterning accuracy of the composition and the like.
From the viewpoint of heat resistance of the composition, the polymerizable component B preferably contains a high molecular weight compound as the polymerizable compound B.
From the viewpoint of the balance between the patterning accuracy and heat resistance of the composition, the polymerizable component B preferably contains both a low molecular weight compound and a high molecular weight compound as the polymerizable compound B.
More specifically, when the polymerizable component B is a radically polymerizable component, it is preferable to contain a low molecular weight compound as the radically polymerizable compound from the viewpoint of patterning accuracy and the like, and the patterning accuracy and heat resistance are improved. From the viewpoint, it is preferable that the radically polymerizable compound contains both a low molecular weight compound and a high molecular weight compound.
The molecular weight of the low molecular weight compound may be any as long as it can obtain desired patterning accuracy and the like. For example, it can be less than 1000, preferably 50 or more and 500 or less, and particularly 50 or more and 300 or less. Is preferable.
The molecular weight of the high molecular weight compound may be any as long as it can obtain desired heat resistance and the like. For example, it can be 1000 or more, preferably 1000 or more and 100,000 or less, and among them, 1500 or more and 50,000. It is preferably less than or equal to, and particularly preferably 2000 or more and 10000 or less.
Hereinafter, the molecular weight indicates the weight average molecular weight (Mw) when the compound is a polymer.

The weight average molecular weight can be determined by gel permeation chromatography (GPC) as a standard polystyrene conversion value. For the weight average molecular weight Mw, for example, GPC (LC-2000plus series) manufactured by JASCO Corporation is used, the elution solvent is tetrahydrofuran, and the polystyrene standard for the calibration curve is Mw1110000, 707000, 397000, 189000, 98900, 37200, 13700, 9490, It can be obtained by measuring 5430, 3120, 1010, 589 (TSKgel standard polystyrene manufactured by Toso) and measuring columns as KF-804, KF-803, KF-802 (manufactured by Showa Denko). The measurement temperature can be 40 ° C. and the flow velocity can be 1.0 mL / min.

The content of the high molecular weight compound is not particularly limited as long as it can be made excellent in patterning accuracy and heat resistance. For example, from the viewpoint of the balance between patterning accuracy and heat resistance, it is appropriate. It is to be adjusted.
Specifically, the content of the high molecular weight compound is preferably 1 part by mass or more and 90 parts by mass or less, particularly 1 part by mass or more and 80 parts by mass or less in 100 parts by mass of the polymerizable component B. Is preferable. This is because the composition is excellent in patterning accuracy and heat resistance.
In the present invention, from the viewpoint of making the composition more excellent in heat resistance, the content of the high molecular weight compound is preferably 30 parts by mass or more in 100 parts by mass of the polymerizable component B. Among them, 50 parts by mass or more is preferable, and 70 parts by mass or more is preferable.
From the viewpoint of making the composition excellent in coatability, the content of the high molecular weight compound is preferably 60 parts by mass or less, particularly 40 parts by mass, in 100 parts by mass of the polymerizable component B. The amount is preferably 2 parts or less, and particularly preferably 20 parts by mass or less.
Further, from the viewpoint of making the composition more excellent in heat resistance, the content of the high molecular weight compound is 20 parts by mass or more in a total of 100 parts by mass of the compound A and the polymerizable component B. It is preferable that the amount is 50 parts by mass or more and 90 parts by mass or less, and particularly preferably 70 parts by mass or more and 90 parts by mass or less.
From the viewpoint of making the composition excellent in coatability, the content of the high molecular weight compound is preferably 80 parts by mass or less in a total of 100 parts by mass of the compound A and the polymerizable component B. Above all, it is preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less.
The content of the high molecular weight compound is such that when the polymerizable component B contains both a radically polymerizable compound and a cationically polymerizable compound, the high molecular weight compound as the radically polymerizable compound and the high molecular weight as the cationically polymerizable compound. It shows the total content of the compounds.

3. 3. Polymerization Initiator The composition preferably contains a polymerization initiator capable of polymerizing the polymerizable components B with each other.
This is because it becomes easy to form a patterned cured product with high patterning accuracy by using the above composition.
Such a polymerization initiator can be appropriately selected depending on the type of the polymerizable component B.
When the polymerizable component B contains a radical-polymerizable compound and a cationically polymerizable compound, the above-mentioned polymerization initiator can use a radical polymerization initiator and a cationic polymerization initiator, respectively.

The content of the polymerization initiator may be any composition that is superior in patterning accuracy and heat resistance.
The content may be, for example, 0.01 part by mass or more and 30 parts by mass or less, and 0.1 part by mass or more and 20 parts by mass or less in 100 parts by mass of the solid content of the composition of the present invention. It is preferable that the amount is 2 parts by mass or more and 10 parts by mass or less. This is because the above content makes the composition more excellent in patterning accuracy and heat resistance.
The content of the polymerization initiator may be any as long as it can form a composition having excellent patterning accuracy and heat resistance, but it should be 10 parts by mass or more and 700 parts by mass or less with respect to 100 parts by mass of compound A. It is preferable that the amount is 15 parts by mass or more and 650 parts by mass or less, and 20 parts by mass or more and 600 parts by mass or less is preferable. This is because when the content is in the above range, it becomes easy to form a composition having excellent patterning accuracy and heat resistance.
The content of the polymerization initiator may be one that can form a composition having excellent patterning accuracy and heat resistance, but is 0.1 part by mass or more and 50 parts by mass with respect to 100 parts by mass of the polymerizable component B. It is preferably 5 parts by mass or less, preferably 0.5 part by mass or more and 45 parts by mass or less, and preferably 1 part by mass or more and 40 parts by mass or less. This is because when the content is in the above range, it becomes easy to form a composition having excellent patterning accuracy and heat resistance.

(1) Radical Polymerization Initiator The radical polymerization initiator may be any one capable of generating radicals and polymerizing a radically polymerizable component.

As such a radical polymerization initiator, either a photoradical polymerization initiator or a thermal radical polymerization initiator can be used, but from the viewpoint of more effectively exerting the effect of being excellent in patterning accuracy and the like, light is used. It is preferably a radical polymerization initiator.
Examples of the photoradical polymerization initiator include benzoins such as benzoin, benzoin methyl ether and benzoin propyl ether, and benzoin butyl ether; benzyl ketals such as benzyl dimethyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and the like. 2,2-Diethoxy-2-phenylacetophenone, 1-benzyl-1-dimethylamino-1- (4'-morpholinobenzoyl) propane, 2-morpholyl-2- (4'-methylmercapto) benzoylpropane, 2-methyl -1- [4- (Methylthio) phenyl] -2-morpholino-propane-1-one, 1-hydroxycyclohexylphenylketone, 1-hydroxy-1-benzoylcyclohexane, 2-hydroxy-2-benzoylpropane, 2-hydroxy Acetphenones such as -2- (4'-isopropyl) benzoylpropane, N, N-dimethylaminoacetophenone, 1,1-dichloroacetophenone, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyl dichloromethane; 2-methylanthraquinone, 1 -Antraquinones such as chloroanthraquinone and 2-amylanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; acetophenone dimethylketal, benzyldimethylketal Ketals such as benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone and 4-benzoyl-4'-benzophenone such as methyldiphenylsulfide; 2,4,6- Oxides such as trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphinoxide; carbazoles such as 3- (2-methyl-2-morpholinopropionyl) -9-methylcarbazole; benzyl, Α-Dicarbonyls such as methyl benzoylate; JP-A-2000-80068, JP-A-2001-233842, JP-A-2005-97141, JP-A-2006-516246, Patent No. 3860170, Patent No. 3790088, WO2006 / 018973, JP2011-132215, WO2015 / 15 Oxim esters such as the compounds described in JP No. 2153; p-methoxyphenyl-2,4-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-Phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-butoxystylyl) -s-triazine, etc. Triazines; benzoyl peroxide, 2,2'-azobisisobutyronitrile, ethylanthraquinone, 1,7-bis (9'-acrydinyl) heptane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethyl Thioxanthone, benzophenone, phenylbiphenyl ketone, 4-benzoyl-4'-methyldiphenylsulfide, 2- (p-butoxystylyl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylaclydin, 9, Examples thereof include 10-dimethylbenzphenazine, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, thioxanthone / amine and the like.

Examples of the thermal radical polymerization initiator include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, and 4,4-. Peroxides such as di (t-butylperoxy) butylvalerate and dicumyl peroxide; azo compounds such as 2,2'-azobisisobutyronitrile; tetramethyltiraum disulfide and the like can be mentioned.

(2) Cationic Polymerization Initiator The above-mentioned cationic polymerization initiator may be any compound that can generate an acid under predetermined conditions. For example, an acid can be obtained by irradiation with light such as ultraviolet irradiation. A photocationic polymerization initiator capable of generating an acid and a thermal cationic polymerization initiator capable of generating an acid by heat can be used.
As the cationic polymerization initiator, at least one of the photocationic polymerization initiator and the thermal cationic polymerization initiator can be used, but from the viewpoint of easy curing, the composition is adjacent to the composition at the time of curing. A photocationic polymerization initiator is preferable from the viewpoint that damage due to heat to the peripheral members used can be reduced and the degree of freedom in selecting the peripheral members is increased. Further, the photocationic polymerization initiator has an advantage that the curing rate is high.
Further, the cationic polymerization initiator is preferably a thermal cationic polymerization initiator from the viewpoint of facilitating the formation of a cured product even in a place where light is difficult to reach.

As such a cationic polymerization initiator and the like, the cationic polymerization initiator and the like described in JP-A-2016-17609 can be used.

4. Polymer having a carboxyl group From the viewpoint of making the composition excellent in developability, it is preferable to contain a polymer having a carboxyl group. This is because the composition becomes more excellent in patterning accuracy by containing the polymer.

The polymer having a carboxyl group may be any one having a structural unit having a carboxyl group (hereinafter, referred to as "structural unit (U1)"), and is not particularly limited, but is further limited to a methacryloyl group, an acryloyl group, and vinyl. A structural unit having a crosslinkable group such as a group, an epoxy group, an oxetanyl group, a vinyl ether group, a mercapto group, an isocyanate group (hereinafter referred to as "structural unit (U2)"), and a structural unit having a silyl group (hereinafter "structure"). It is preferable to have a structural unit selected from the unit (U3).
The polymer having a carboxyl group may have a structural unit other than the structural units (U1) to (U3) (hereinafter, referred to as "structural unit (U4)").

The structural unit (U1) is a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as "compound (u1)"). Is preferable.
Examples of the compound (u1) include monocarboxylic acids, dicarboxylic acids, and anhydrides of dicarboxylic acids. Examples of the monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and 2-methacryloyloxyethyl hexa. Hydrophthalic acid, etc .;
Examples of the dicarboxylic acid include maleic acid, fumaric acid, citraconic acid and the like;
Examples of the dicarboxylic acid anhydride include the above-mentioned dicarboxylic acid anhydride and the like.

Of these, acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid or maleic anhydride are selected from the viewpoints of copolymerizability and solubility of the obtained copolymer in the developing solution. preferable.
Compound (u1) can be used alone or in admixture of two or more.

The structural unit (U2) is preferably a structural unit derived from a polymerizable unsaturated compound having an epoxy group or an oxetanyl group (hereinafter, referred to as “compound (u2)”).
The compound (u2) is preferably at least one selected from the group consisting of a polymerizable unsaturated compound having an epoxy group and a polymerizable unsaturated compound having an oxetanyl group.

Examples of the polymerizable unsaturated compound having an epoxy group include (meth) acrylate oxylanyl (cyclo) alkyl ester, α-alkyl acrylate oxylanyl (cyclo) alkyl ester, and a glycidyl ether compound having a polymerizable unsaturated bond. ;
Examples of the polymerizable unsaturated compound having an oxetanyl group include (meth) acrylic acid ester having an oxetanyl group.

Specific examples of the above compound (u2) include
Examples of the (meth) acrylate oxylanyl (cyclo) alkyl ester include (meth) glycidyl acrylate, 2-methylglycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and (meth) acrylate 3, 4-epoxybutyl, (meth) acrylic acid 6,7-epoxyheptyl, (meth) acrylic acid 3,4-epoxycyclohexyl, (meth) acrylic acid 3,4-epoxycyclohexylmethyl, 3,4-epoxytricyclo [ 5.2.1.02.6] Decyl (meth) acrylate, etc.;
Examples of α-alkylacrylic acid oxylanyl (cyclo) alkyl esters include α-ethylacrylic acid glycidyl, α-n-propylacrylic acid glycidyl, α-n-butylacrylic acid glycidyl, and α-ethylacrylic acid 6,7-epoxy. Heptyl, α-ethylacrylic acid 3,4-epoxycyclohexyl, etc.;
Examples of the glycidyl ether compound having a polymerizable unsaturated bond include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like;
Examples of the (meth) acrylic acid ester having an oxetanyl group include 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) acryloyloxymethyl) -3-ethyloxetane, and 3-((meth) acryloyloxy). Methyl) -2-methyloxetane, 3-((meth) acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3-((meth) acryloyloxyethyl) oxetane, 3-methyl-3- (meth) acryloyl Oxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane and the like can be mentioned respectively.

Among these specific examples, in particular, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxytricyclo [5.2. 1.02.6] decylmethacrylate, 3,4-epoxytricyclo [5.2.1.02.6] decylacrylate, 3-methacryloyloxymethyl-3-ethyloxetane, 3-methyl-3-methacryloyloxy Methyloxetane or 3-ethyl-3-methacryloyloxymethyloxetane is preferable from the viewpoint of polymerizable property.
Compound (u2) can be used alone or in admixture of two or more.

Among the above structural units (U2), as the structural unit having a methacryloyl group or an acryloyl group as the crosslinkable group, a structural unit having a (meth) acryloyloxy group can be preferably used.
The structural unit having a (meth) acryloyloxy group is obtained by reacting a (meth) acrylic acid ester having an epoxy group with a carboxyl group in a polymer. The structural unit having a (meth) acryloyloxy group after the reaction is preferably a structural unit represented by the following formula (U2-1).

（式中、Ｒ^１０００およびＲ^１００１は、それぞれ独立して水素原子又はメチル基であり、Ｒ^１００２は、下記式（α）又は下記式（β）で表される２価の基であり、ｃは、１〜６の整数であり、＊は結合箇所を表す。）

(In the formula, R ¹⁰⁰⁰ and R ¹⁰⁰¹ are independent hydrogen atoms or methyl groups, respectively, and R ¹⁰⁰² is a divalent group represented by the following formula (α) or the following formula (β), c. Is an integer from 1 to 6, and * represents the joint location.)

（式中、Ｒ^１００３は、水素原子又はメチル基であり、＊は、結合箇所を表す。）

(In the formula, R ¹⁰⁰³ is a hydrogen atom or a methyl group, and * represents a bond site.)

Regarding the structural unit represented by the above formula (U2-1), for example, when a compound having a carboxyl group is reacted with a compound such as glycidyl methacrylate or 2-methylglycidyl methacrylate, the formula (U2-1) is used. R ^{1002 in} ) is given by the equation (α). On the other hand, when 3,4-epoxycyclohexylmethyl methacrylate is reacted with the copolymer having a carboxyl group, R ¹⁰⁰² in the formula (U2-1) becomes the formula (β).

In the above-mentioned reaction between a carboxyl group and an unsaturated compound such as an (meth) acrylic acid ester having an epoxy group in the polymer, a weight containing a polymerization inhibitor is preferably used in the presence of a suitable catalyst, if necessary. An unsaturated compound having an epoxy group is added to the combined solution, and the mixture is stirred under heating for a predetermined time. Examples of the catalyst include tetrabutylammonium bromide and the like. Examples of the polymerization inhibitor include p-methoxyphenol and the like. The reaction temperature is preferably 70 ° C to 100 ° C. The reaction time is preferably 8 to 12 hours.

In the structural unit ratio of the polymer having a carboxyl group, the content ratio of the structural unit having a (meth) acryloyloxy group as a crosslinkable group is 10 mol% to 70 mol of all the structural units of the polymer having a carboxyl group. %, More preferably 20 mol% to 50 mol%.
When the ratio of structural units having a (meth) acryloyloxy group is within the above range, heat resistance and development defects during development can be reduced, and the generation of development residues can be suppressed.

The structural unit (U3) is preferably a structural unit derived from a polymerizable unsaturated compound having a silyl group (hereinafter, referred to as “compound (u3)”).

Examples of the compound (u3) include 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, and 3- (meth). ) Acryloyloxypropyltriethoxysilane and the like can be mentioned.
The above compound (u3) can be used alone or in combination of two or more.

The structural unit (U4) is a structural unit other than the above (U1) to (U3), and is a polymerizable unsaturated compound other than the above (u1) to (u3) (hereinafter, referred to as “compound (u4)”). It is preferably a structural unit derived from.
Examples of the compound (u4) include (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid aryl ester, (meth) acrylic acid aralkyl ester, unsaturated dicarboxylic acid dialkyl ester, and the like. Examples thereof include (meth) acrylic acid esters, vinyl aromatic compounds, conjugated diene compounds and other polymerizable unsaturated compounds having an oxygen-containing complex 5-membered ring or an oxygen-containing complex 6-membered ring. Specific examples of these include, as (meth) acrylic acid alkyl esters, for example, methyl acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, (. Meta) sec-butyl acrylate, t-butyl (meth) acrylate, etc.;
Examples of the (meth) acrylic acid cycloalkyl ester include (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-methylcyclohexyl, and (meth) acrylic acid tricyclo [5.2.1.102,6] decane-8-. Il, 2- (tricyclo [5.2.1.02,6] decane-8-yloxy) ethyl (meth) acrylate, isobolonyl (meth) acrylate, etc.;
As the (meth) acrylic acid aryl ester, for example, phenyl acrylate or the like;
As the (meth) acrylic acid aralkyl ester, for example, benzyl (meth) acrylic acid and the like;
As unsaturated dicarboxylic acid dialkyl esters, for example, diethyl maleate, diethyl fumaric acid, etc.;
Examples of the (meth) acrylic acid ester having an oxygen-containing complex 5-membered ring or an oxygen-containing complex 6-membered ring include (meth) acrylate tetrahydrofuran-2-yl, (meth) acrylate tetrahydropyran-2-yl, and (meth). ) 2-Methyltetrahydropyran-2-yl acrylate, etc.;
As the vinyl aromatic compound, for example, styrene, α-methylstyrene and the like;
As the conjugated diene compound, for example, 1,3-butadiene, isoprene and the like;
Examples of other polymerizable unsaturated compounds include 2-hydroxyethyl (meth) acrylate, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide, respectively.

The compound (u4) includes n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, and tricyclo methacrylate [5.2.1.02,6] decane-8 from the viewpoint of copolymerization reactivity. -Il, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene and the like are preferable.
The above compound (u4) can be used alone or in combination of two or more.

The above-mentioned polymer having a carboxyl group can be synthesized by copolymerizing a mixture of polymerizable unsaturated compounds containing the above-mentioned compounds (u1) to (u4) in the following ratios, respectively.
Compound (u1): preferably 0.1 mol% to 30 mol%, more preferably 1 mol% to 20 mol%, still more preferably 5 mol% to 15 mol%.
Compound (u2): preferably 1 mol% to 95 mol%, more preferably 10 mol% to 60 mol%, still more preferably 20 mol% to 30 mol%.
Compound (u3): preferably 50 mol% or less, more preferably 1 mol% to 40 mol%, still more preferably 10 mol% to 30 mol%.
Compound (u4): preferably 80 mol% or less, more preferably 1 mol% to 60 mol%, still more preferably 25 mol% to 50 mol%.

Further, the (meth) acryloyloxy group is formed by reacting the carboxyl group in the structural unit derived from the compound (u1) in the obtained copolymer with the (meth) acrylic acid ester having an epoxy group. It can have a structural unit to have.

A polymerizable composition containing a polymer having a carboxyl group obtained by copolymerizing a mixture of a polymerizable unsaturated compound containing the compound (u1) to the compound (u4) in the above range has good coatability. Since high resolution is achieved without impairing the above, it is preferable because a cured film having a highly balanced characteristic balance can be provided even with a high-definition pattern.

The weight average molecular weight (Mw) of the polymer having a carboxyl group may be any as long as it can obtain the desired developability. For example, "(1) Radical" in "2. Polymeric component having thiol reactivity" described above. It can be the same as the molecular weight of the high molecular weight compound in the "polymerization component". By using the above polymer, high resolution is achieved without impairing good coatability, so that a cured film having a highly balanced characteristic balance can be provided even in a high-definition pattern. It becomes.

The polymer having a carboxyl group can be produced by polymerizing a mixture of the above-mentioned polymerizable unsaturated compounds in a suitable solvent, preferably in the presence of a radical polymerization initiator.

Examples of the solvent used for the above polymerization include diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and dipropylene glycol monomethyl. Examples thereof include ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol, 3-methoxybutanol and the like. These solvents can be used alone or in admixture of two or more.

The radical polymerization initiator is not particularly limited, and is, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2. '-Azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), dimethyl-2,2'-azobis (2-methylpropionate), 2, Examples of azo compounds such as 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) can be mentioned. These radical polymerization initiators can be used alone or in admixture of two or more.

Preferred examples of the polymer having a carboxyl group include the following polymers U-1 and U-2.

[Polymer U-1]
A flask equipped with a cooling tube and a stirrer was charged with 4 parts by mass of 2,2'-azobisisobutyronitrile and 190 parts by mass of propylene glycol monomethyl ether acetate, followed by 55 parts by mass of methacrylic acid and 45 parts by mass of benzyl methacrylate. In addition, 2 parts by mass of α-methylstyrene dimer as a molecular weight modifier was charged, and the temperature of the solution was raised to 80 ° C. while gently stirring. After holding at 80 ° C. for 4 hours, the temperature of the solution is raised to 100 ° C., and this temperature is held for 1 hour for polymerization to obtain a solution containing a copolymer. Next, 1.1 parts by mass of tetrabutylammonium bromide and 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor were added to the solution containing this copolymer, and the mixture was stirred at 90 ° C. for 30 minutes in an air atmosphere, and then methacrylic acid. A polymer U-1 having a weight average molecular weight of Mw9000 obtained by adding 74 parts by mass of glycidyl acid acid and reacting at 90 ° C. for 10 hours can be mentioned.
The polymer U-1 has a structural unit (U1), a structural unit (U2), and a structural unit (U4).

[Polymer U-2]
A flask equipped with a cooling tube and a stirrer was charged with 5 parts by mass of 2,2'-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate, and further 18 parts by mass of methacrylic acid and tricyclo methacrylate [5.2]. 1.02.6] 25 parts by mass of decane-8-yl, 5 parts by mass of styrene, 20 parts by mass of 3-acryloxipropyltrimethoxysilane and 32 parts by mass of glycidyl methacrylate were charged and replaced with nitrogen, and then gently stirred. At the same time, the temperature of the solution is raised to 80 ° C. A polymer U-2 having a weight average molecular weight of Mw12000 obtained by holding this temperature for 5 hours and polymerizing can be mentioned.
The polymer U-2 has a structural unit (U1), a structural unit (U2), a structural unit (U3), and a structural unit (U4).

The content of the polymer having a carboxyl group is appropriately selected according to the purpose of use and is not particularly limited, but is, for example, 10 parts by mass or more and 90 parts by mass or less in 100 parts by mass of the solid content of the composition. Can be done.
The total content of the polymer having a carboxyl group and the polymerizable component B is appropriately selected and not particularly limited according to the purpose of use thereof, but is, for example, 10 in 100 parts by mass of the solid content of the composition. It can be equal to or more than 99 parts by mass and not more than 99 parts by mass.

5. Other Ingredients In addition to the compound A, the polymerizable component B and the polymerization initiator, the composition may contain other components, if necessary.
Examples of the other components include a polymer having no polymerizable group, a solvent that dissolves or disperses each of the above components, a colorant, and the like.

(1) Polymer having no polymerizable group The above-mentioned polymer does not have a polymerizable group.
Here, examples of the polymerizable group include a radically polymerizable group and a cationically polymerizable group.
Examples of such polymers include polycarbonate (PC), polyethylene terephthalate (PET), polyether sulfone, polyvinyl butyral, polyphenylene ether, polyamide, polyamideimide, polyetherimide, norbornene resin, acrylic resin, and methacrylic resin. , Isobutylene anhydride maleic acid copolymer resin, cyclic olefin resin, polyvinyl alcohol, polyethylene glycol, polynivir pyrrolidone and other thermoplastic resins can be mentioned.
As the polymer, a polymer of the polymerizable component B can also be used.
Further, as the polymer, among the polymers having a carboxyl group, those which do not contain a structural unit having a crosslinkable group can also be used.

The weight average molecular weight (Mw) of the polymer is appropriately set according to the use of the composition and the like, and can be, for example, 1500 or more, and 1500 or more and 300,000 or less.
The content of the polymer is appropriately selected according to the purpose of use and is not particularly limited, but can be, for example, 10 parts by mass or more and 90 parts by mass or less in 100 parts by mass of the solid content of the composition.
The total content of the polymer and the polymerizable component B is appropriately selected according to the purpose of use and is not particularly limited. For example, a total of 10 parts by mass or more and 99 parts by mass or more in 100 parts by mass of the solid content of the composition. It can be less than or equal to parts by mass.

(2) Solvent The solvent is liquid at 25 ° C. and atmospheric pressure, and can disperse or dissolve each component of the composition.
Further, the solvent does not have a polymerizable group such as a radical polymerizable group or a cationically polymerizable group.
Therefore, for example, among the polymerizable components B, those which are liquid at 25 ° C. and atmospheric pressure do not correspond to the above solvent.
Examples of such a solvent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxy. Ether solvents such as ethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, Ester solvent such as texanol; Cellosolve solvent such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol solvent such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene Ether ester solvents such as glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, ethoxyethyl ether propionate; BTX solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; terpen solvents such as terepine oil, D-lymonen and pinen; mineral spirit, swazole # 310 ( Cosmo Matsuyama Petroleum Co., Ltd.), Solbesso # 100 (Exxon Chemical Co., Ltd.) and other paraffinic solvents; Halogenized aromatic hydrocarbon solvent; carbitol solvent; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N, N-dimethylformamide; N, N-dimethylacetamide; N-methylpyrrolidone; dimethylsulfoxide, etc. Organic solvent of.
Further, the solvent may contain water.
Among these, ketones, ether ester solvents and the like, particularly organic solvents such as propylene glycol-1-monomethyl ether-2-acetate (hereinafter, also referred to as "PGMEA" or "propylene glycol monomethyl ether acetate") and cyclohexanone are used. , Preferable from the viewpoint of good compatibility with compound A and the like.
The above solvent can be used as one kind or a mixed solvent of two or more kinds.

The content of the solvent may be any composition that is superior in patterning accuracy and heat resistance.
The content can be, for example, 10 parts by mass or more and 95 parts by mass or less, preferably 40 parts by mass or more and 95 parts by mass or less, and 60 parts by mass or more in 100 parts by mass of the composition of the present invention. It is preferably 90 parts by mass or less. This is because the composition has excellent coatability when the content is as described above.

(3) Silane Coupling Agent The above composition may contain a silane coupling agent, if necessary.
As such a silane coupling agent, one having a molecular weight of 100 or more and 1000 or less can be used. For example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, KBE-9007, KBM-502, etc. A silane coupling agent having an isocyanate group, a methacryloyl group, and an epoxy group such as KBE-403 is preferably used.
Even if the silane coupling agent contains a methacryloyl group, an epoxy group, or the like, it is not contained in the polymerizable component B.

(4) Colorant The above composition may contain a colorant, if necessary.
Examples of the colorant include pigments, dyes, natural pigments and the like. These colorants can be used alone or in admixture of two or more.

Examples of the pigment include nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; isoindolin compounds; quinacridone compounds; antanthurone compounds; perinone. Compounds; perylene compounds; diketopyrrolopyrrole compounds; thioindigo compounds; dioxazine compounds; triphenylmethane compounds; quinophthalone compounds; naphthalenetetracarboxylic acids; azo dyes, cyanine dye metal complex compounds; lake pigments; furnace method, channel method or thermal Carbon black obtained by the method, or carbon black such as acetylene black, ketjen black, or lamp black; the above carbon black adjusted or coated with an epoxy resin, the above carbon black is previously dispersed in a resin in a solvent, and 20 ~ 200 mg / g of resin adsorbed, the above carbon black treated with acidic or alkaline surface, average particle size of 8 nm or more and DBP oil absorption of 90 ml / 100 g or less, CO in volatile matter at 950 ° C. And the total amount of oxygen calculated from _{CO 2} ^{is 9 mg or more per 100 m 2 of} carbon black surface area; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene. Aniline black, pigment black 7, titanium black, perylene black, lactam black, cyanine black; chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate ultramarine, navy blue, ultramarine, cerulean Organic or inorganic pigments such as blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, synthetic iron black, and amber can be used. These pigments can be used alone or in admixture.

As the above pigment, a commercially available pigment can also be used. For example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71, 72; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185, 211, 215, 231; Pigment Green 7, 10, 36, 58, 59, 62, 63; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50; Pigment Violet 19, 23, 29 and the like.

Examples of the above dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acrydin dyes, stillben dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, and phthalocyanine dyes. , Dyes such as cyanine dyes, etc., and these may be used as a mixture of a plurality.

The content of the colorant may be any as long as it can obtain a cured product having a desired color, and is preferably 1 part by mass or more and 80 parts by mass or less in 100 parts by mass of the solid content of the composition. Among them, it is preferably 5 parts by mass or more and 60 parts by mass or less, and particularly preferably 10 parts by mass or more and 50 parts by mass or less.
The content of the colorant may be one that can obtain a cured product having a desired color, and is, for example, 1 part by mass or more and 350 parts by mass or less with respect to 100 parts by mass of the polymerizable component B. Of these, it is preferably 10 parts by mass or more and 250 parts by mass or less, and particularly preferably 20 parts by mass or more and 200 parts by mass or less.

(5) Additives Examples of the other components include dispersants, chain transfer agents, sensitizers, surfactants, silane coupling agents, melamines, etc. that disperse colorants, inorganic compounds, colorants, inorganic compounds, etc. Additives can be mentioned.
As the additive, a known material can be used, and for example, those described in International Publication No. 2014/021023 can be used.
As the additive, an ultraviolet absorber, an antioxidant and the like can also be used.
As the ultraviolet absorber, a latent ultraviolet absorber and a latent antioxidant that exhibit an ultraviolet absorbing ability and an antioxidant function by heat treatment or the like can also be used.
As such a latent ultraviolet absorber and a latent antioxidant, for example, those described as latent additives described in International Publication No. 2014/021023 can be used.

The total content of the additives can be 30 parts by mass or less in 100 parts by mass of the solid content of the composition.

6. Production method The production method of the composition may be a method in which the above components can be blended in a desired content, or a method in which the above components are added and mixed at the same time, and the components are sequentially added. It may be a method of mixing while mixing.

The use of the composition and the like can be the same as the use of the composition to which the thiol generator described in the section of "A. Compound" is added.

D. Cured product Next, the cured product of the present invention will be described.
The cured product of the present invention is characterized by being a cured product of the above-mentioned composition.

According to the present invention, the cured product is excellent in patterning accuracy and heat resistance by using the above composition.

The cured product of the present invention uses the above-mentioned composition.
Since the content of the composition can be the same as that described in the section of "C. Composition" above, the description thereof is omitted here.

The cured product has a polymer in which the polymerizable components B are polymerized with each other.

The residual ratio of the unreacted polymerizable component B contained in the cured product is appropriately set according to the intended use of the cured product, and is, for example, 10 parts by mass or less in 100 parts by mass of the cured product. Yes, it is preferably 1 part by mass or less. This is because the cured product has excellent heat resistance.

Compound A contained in the cured product, which thiol group is protected by a protecting group R ^1, which protecting group R ¹ is a thiol group by detachment occurs, and crosslinking the polymerizable component B together It may be a thing.
Here, the term "compound A cross-links the above-mentioned polymerizable components B" means that ^{the compound A after desorption of R 1} cross-links the polymerizable components B.
Further, the cross-linking refers ^{to a state in which the thiol group generated from the compound A by R 1} desorption forms a covalent bond with the thiol-reactive group of the polymerizable component B by a thiol-ene reaction or the like. ..
In the present invention, it is preferable that the compound A crosslinks the polymerizable components B with each other. This is because the cured product has excellent heat resistance.
The polymerizable component B to be crosslinked by the compound A contains at least one of the following (1) and (2).
(1) Unreacted polymerizable component B remaining without polymerization between the polymerizable components B
(2) Among the polymers in which the polymerizable components B are polymerized with each other, those having a thiol-reactive group

The plan-view shape of the cured product can be appropriately set according to the intended use of the cured product, and is preferably a pattern such as a dot shape or a line shape. This is because the effect of being able to form a composition having excellent patterning accuracy and heat resistance of the present invention can be more effectively exhibited.

The uses and the like of the cured product can be the same as those described in the section of "A. Compound".

The method for producing the cured product is not particularly limited as long as the cured product of the composition can be formed into a desired shape.
As such a manufacturing method, for example, the manufacturing method described in the section "E. Manufacturing method of cured product" described later can be used.

E. Method for producing a cured product Next, a method for producing a cured product of the present invention will be described.
The production method of the present invention includes a step of cross-linking.
Hereinafter, each step of the production method of the present invention will be described in detail.

1. 1. Cross-linking step The cross-linking step in the production method of the present invention is a step of cross-linking the polymerizable components B with each other by the compound represented by the general formula (A).
Method as a method of cross-linking in this step, release the protective group R ¹ from the compound A de by thiol groups generated as long as it can crosslink the polymerizable component B together, for example, the heat treatment of the above-mentioned compound A Can be mentioned.
The heating temperature and the like for heating the compound A ^{may be any temperature conditions such as the temperature at which R 1} can be desorbed from the compound A, and can be, for example, the same as the contents described in the above section “A. Compound”. ..
As a method for heat-treating the compound A, a method of heating the composition or a cured product thereof (composition after the polymerization step described later) using a known heating means such as an oven can be used.
Further, the above-mentioned cross-linking step may be performed at the same time as the post-baking step described later.
The polymerizable component B crosslinked by this step contains at least one of the following (1) and (2) when this step is carried out after the polymerization step described later.
(1) Unreacted polymerizable component B remaining without polymerization between the polymerizable components B
(2) Among the polymers in which the polymerizable components B are polymerized with each other, those having a thiol-reactive group

2. Polymerization Step The method for producing a cured product preferably includes a step of polymerizing the polymerizable components B together. This is because the patterning accuracy and heat resistance are improved.
The method for polymerizing the polymerizable components B in this step may be any method as long as the polymerizable components B can be polymerized with each other. For example, the composition containing the polymerizable component B and the polymerization initiator is used. The method can be mentioned.
The above polymerization method differs depending on the type of radical polymerization initiator.
For example, when the composition contains a photopolymerization initiator such as a photoradical polymerization initiator and a photocationic polymerization initiator as the polymerization initiator, the composition is irradiated with light to bring the polymerizable components B together. A method of polymerization can be used.
The light irradiated to the composition may include light having a wavelength of 300 nm to 450 nm.
Examples of the light source for light irradiation include ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc and the like.
Laser light may be used as the light to be irradiated. As the laser light, one containing light having a wavelength of 340 to 430 nm can be used.
As the light source of the laser light, a light source in the visible to infrared region such as an argon ion laser, a helium neon laser, a YAG laser, and a semiconductor laser can also be used.
When these lasers are used, the composition may contain a sensitizing dye that absorbs the visible to infrared region.

In the above polymerization method, for example, when the composition contains a thermal polymerization initiator such as a thermal radical polymerization initiator or a thermal cationic polymerization initiator as the polymerization initiator, the composition is heat-treated to be polymerizable. A method of polymerizing the components B to each other can be used.
The heating temperature may be 60 ° C. or higher, preferably 100 ° C. or higher and 300 ° C. or lower, as long as the composition can be stably cured.
The heating time can be about 10 seconds to 3 hours.

The type of the polymerization method may include only one type, or may include two or more types.

The timing of carrying out the polymerization step may be either before or after the cross-linking step, but from the viewpoint that a patterned cured product can be produced with high patterning accuracy, the cross-linking step It is preferable to be in front of.

3. 3. Other Steps The method for producing a cured product may include, if necessary, other steps in addition to the above-mentioned cross-linking step and polymerization step.
The other steps include a development step of removing the unpolymerized portion in the coating film of the composition to obtain a patterned cured product after the polymerization step, and a post-baking process in which the cured product is heat-treated after the polymerization step. Examples thereof include a step, a prebaking step of heat-treating the composition to remove the solvent in the composition before the polymerization step, a step of forming a coating film of the composition before the polymerization step, and the like. can.

Examples of the method for removing the unpolymerized portion in the development step include a method of applying an alkaline developer to the unpolymerized portion.
As the alkaline developer, those generally used as an alkaline developer such as an aqueous solution of tetramethylammonium hydroxide (TMAH) and an aqueous solution of potassium hydroxide can be used.
The timing of carrying out the development step may be after the polymerization step, but is preferably before the desorption step from the viewpoint that a patterned cured product can be produced with high patterning accuracy. ..
The heating conditions in the post-baking step may be any one that can improve the strength of the cured product obtained by the polymerization step, for example, 100 ° C. or higher and 300 ° C. or lower, and 120 ° C. or higher. It is preferably 150 ° C. or higher, and can be 200 ° C. or higher and 250 ° C. or lower for 20 minutes to 90 minutes. This is because when the post-baking temperature is in the above-mentioned range, it becomes easy to carry out the post-baking step and the cross-linking step at the same time after the polymerization step.
The heating conditions in the prebaking step may be any one that can remove the solvent in the composition, and can be, for example, 30 seconds to 300 seconds at 70 ° C. or higher and 150 ° C. or lower.
Further, it is preferable that the heating conditions in the prebaking step are performed at a temperature equal to or lower than the desorption temperature of the compound A, for example, from the viewpoint of facilitating the step of polymerizing and the step of cross-linking in this order. From such a viewpoint, the heating conditions in the prebaking step are preferably less than 150 ° C., particularly preferably less than 120 ° C., particularly preferably less than 100 ° C., and 90 ° C. or lower. It is preferable to have.
As a method of applying the composition in the step of forming the coating film, known methods such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, and immersion can be used.
The coating film can be formed on a substrate.
The base material can be appropriately set according to the intended use of the cured product, and examples thereof include soda glass, quartz glass, semiconductor substrates, metals, paper, plastics, and the like.
Further, the cured product may be formed on a base material and then peeled off from the base material, or may be transferred from the base material to another adherend and used.

4. Others The cured product produced by the above-mentioned production method, its use, and the like can be the same as those described in the above-mentioned "D. Composition" section.

The present invention is not limited to the above embodiment. The above embodiment is an example, and any one having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect and effect is the present invention. It is included in the technical scope of the invention.

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the present invention is not limited to these Examples.

[Example 1]
0.01 mol of polyfunctional thiol (TS-G manufactured by Shikoku Kasei) represented by the following formula (A6-1'), 0.05 mol of di-tert-butyl dicarbonate and 30 g of pyridine are mixed and mixed at room temperature in a nitrogen atmosphere. 0.002 mol of 4-dimethylaminopyridine was added, and the mixture was stirred at 60 ° C. for 3 hours. After cooling to room temperature, the reaction solution was poured into 150 g of ion-exchanged water, 200 g of chloroform was added, and oil-water separation was performed. The organic layer was dried over anhydrous sodium sulfate, dried under reduced pressure at 60 ° C. for 3 hours, and the solvent was distilled off to obtain a compound represented by the following formula (A6-1). ^{It was confirmed by 1 1} H-NMR that the obtained compound was a compound represented by the following formula (A6-1). The results are shown in Table 1 below.

[Examples 2 to 6]
Instead of the polyfunctional thiol represented by the above formula (A6-1'), the following formulas (A4-1'), (A3b-1'), (A2-1'), (A5-1') and ( The following formulas (A4-1), (A3b-1), (A2-1), (A5-1) are the same as in Example 1 except that the polyfunctional thiol represented by A3a-1') is used. ) And (A3a-1) were obtained. The compound obtained is, respectively, the following formula (A4-1), (A3b-1 ), (A2-1), is a compound represented by (A5-1) and ^(A3a-1), 1 Confirmed by 1 H-NMR. Of these, the results for (A4-1), (A2-1), (A5-1) and (A3a-1) are shown in Table 1 below.

[Example 7]
0.06 mol of polyfunctional thiol (TS-G manufactured by Shikoku Kasei) represented by the following formula (A6-1') was placed in a 500 mL two-necked round-bottom flask, dried under reduced pressure and replaced with nitrogen, and then anhydrous. 42 mL of DMF (manufactured by Kanto Chemical Co., Inc.) and 0.83 mL of triethylamine were added, and the mixture was cooled to 0 ° C. Then, 0.24 mol of phenylisocyanate (manufactured by Kanto Chemical Co., Inc.) was added with stirring, and after stirring for 30 minutes, the temperature was returned to room temperature. Further, after stirring for 3 hours, 600 mL of ethyl acetate was added. The organic layer was washed with 300 mL of distilled water. After performing the above washing four times, the organic layer was dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. The reaction product thus obtained was dried under reduced pressure at 60 ° C. for 2 hours to obtain a compound represented by the following formula (A6-2). ^{It was confirmed by 1 1} H-NMR that the obtained compound was a compound represented by the following formula (A6-2).

[Examples 8 to 10]
Instead of the polyfunctional thiol represented by the above formula (A6-1'), the polyfunctional thiol represented by the following formulas (A4-1'), (A2-1') and (A5-1') is used. Compounds represented by the following formulas (A4-2), (A2-2) and (A5-2) were obtained in the same manner as in Example 1. ^{It was confirmed by 1 1} H-NMR that the obtained compounds were the compounds represented by the following formulas (A4-2), (A2-2) and (A5-2), respectively.

[Manufacturing Example 1]
A flask equipped with a cooling tube and a stirrer was charged with 4 parts by mass of 2,2'-azobisisobutyronitrile and 190 parts by mass of propylene glycol monomethyl ether acetate, followed by 55 parts by mass of methacrylic acid and 45 parts by mass of benzyl methacrylate. In addition, 2 parts by mass of α-methylstyrene dimer as a molecular weight modifier was charged, and the temperature of the solution was raised to 80 ° C. while gently stirring. After holding at 80 ° C. for 4 hours, the temperature of the solution was raised to 100 ° C., and this temperature was held for 1 hour for polymerization to obtain a solution containing a copolymer. Next, 1.1 parts by mass of tetrabutylammonium bromide and 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor were added to the solution containing this copolymer, and the mixture was stirred at 90 ° C. for 30 minutes in an air atmosphere, and then methacrylic acid. A polymer U-1 was obtained by adding 74 parts by mass of glycidyl acid acid and reacting at 90 ° C. for 10 hours (solid content concentration = 35.0%). The weight average molecular weight Mw of the polymer U-1 was 9000.
The polymer U-1 has the above-mentioned structural unit (U1), structural unit (U2) and structural unit (U4). The polymer U1 is a radically polymerizable compound and has an acid group.

[Production Example 2] Production of blue pigment dispersion liquid DISPERBYK-161 (8.4 parts by mass; manufactured by Big Chemie Japan) as a dispersant, Pigment Blue 15: 6 (14 parts by mass) as a colorant, and PGMEA (77.6 parts by mass). A blue pigment dispersion liquid (solid content concentration 22.4% by mass, pigment concentration in solid content 62.5% by mass, solvent PGMEA) was produced by dispersing in (parts by mass) using a bead mill.

[Production Example 3] Production of black pigment dispersion liquid DISPERBYK-161 (11.25 parts by mass; manufactured by Big Chemie Japan, solid content concentration 40% by mass) as a dispersant and MA100 (15 parts by mass; manufactured by Mitsubishi Chemical Co., Ltd.) as a colorant. Black pigment) was dispersed in PGMEA (73.75 parts by mass) using a bead mill to disperse a black pigment dispersion (solid content concentration 19.5% by mass, pigment concentration in solid content 76.92% by mass, solvent). PGMEA) was produced.

[Examples 2-1 to 2-22 and Comparative Examples 2-1 to 2-9]
Compound A, thiol compound, polymerizable component B, polymerization initiator, pigment dispersion, coupling agent, and solvent are mixed according to the formulations shown in Tables 2 to 4 below, and the composition is stirred at 25 ° C. for 1 hour. Got
In addition, the following materials were used for each component.
The blending amount in the table represents the mass part of each component.

(Compound A)
A-1: Compound A-1 produced in Example 1 and represented by the general formula (A6-1) A-2: Compound A-2 produced in Example 2 and represented by the general formula (A4-1) 3: Compound A-4 produced by Example 3 and represented by the general formula (A3b-1): Compound A-5 produced by Example 4 and represented by the general formula (A2-1): Compound A-6 produced in Example 5 and represented by the general formula (A5-1): Compound A-7 produced in Example 6 represented by the general formula (A3a-1): Example. Compound A-8 produced by the general formula (A6-2) produced in Example 7: Compound A-9 produced by the general formula (A4-2) produced in Example 8: Example 9. The produced compound represented by the general formula (A2-2) A-10: The compound produced in Example 10 represented by the general formula (A5-2).

(Thiol compound)
A-1': Compound A-2'represented by the above formula (A6-1'): Compound A-3'represented by the above formula (A4-1'): In the above formula (A3b-1') Represented compound A-4': Compound A-5'represented by the above formula (A2-1'): Compound A-6'represented by the above formula (A5-1'): Above formula (A3a- Compound represented by 1')

(Polymerizable component B)
B-1: SPC-3000 (radical polymerizable compound, compound having an acid group (acid group-containing epoxy acrylate), high molecular weight compound; manufactured by Showa Denko, solid content 42.7% by mass, propylene glycol monomethyl ether acetate solution)
B-2: Dipentaerythritol hexaacrylate (radical polymerizable compound, compound without acid group, low molecular weight compound, Kayarad DPHA manufactured by Nippon Kayaku)
B-3: Polymer obtained in Production Example 1 (radical polymerizable compound, compound having an acid group, high molecular weight compound, solid content concentration 35.0% by mass, propylene glycol monomethyl ether acetate solution)

(Initiator)
C-1: Compound represented by the following formula (C1) (photoradical polymerization initiator, oxime esters)
C-2: Compound represented by the following formula (C2) (photoradical polymerization initiator, oxime esters)
C-3: BASF's Irgacure TPO (photoradical polymerization initiator, acylphosphine oxides)
C-4: Compound represented by the following formula (C4) (photoradical polymerization initiator, acetophenones)

(Pigment dispersion)
D-1: Blue pigment dispersion liquid produced in Production Example 2 (solid content concentration 22.4% by mass, pigment concentration in solid content 62.5% by mass, solvent PGMEA)
D-2: Black pigment dispersion liquid produced in Production Example 3 (solid content concentration 19.5% by mass, pigment concentration in solid content 76.92% by mass, solvent PGMEA)

(Silane coupling agent)
E-1: KBE-403 (silane coupling agent, manufactured by Shin-Etsu Chemical)
(solvent)
F-1: Propylene glycol-1-monomethyl ether-2-acetate (solvent)

[evaluation]
The compounds obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Tables 2 to 4.

1. 1. Patterning accuracy The compositions of Examples and Comparative Examples were spin-coated on a glass substrate so that the chromaticity coordinates (x, y) = (0.135, 0.098) after post-baking were obtained, and a hot plate was used. After prebaking at 90 ° C. for 120 seconds, the mixture was cooled at 23 ° C. for 60 seconds.
Then, it was exposed through a photomask (mask opening 30 μm) using an ultra-high pressure mercury lamp (exposure gap 300 μm, exposure amount 40 mJ / cm ² ).
After developing for 60 seconds using a 0.04 mass% KOH aqueous solution as a developing solution, it was washed well with water and post-baked at 230 ° C. for 20 minutes using a clean oven to fix the pattern, and an evaluation sample was obtained.
The obtained pattern was observed with an optical microscope, and the line width of the portion corresponding to the mask opening was measured. With the obtained line width as a reference of the mask opening of 30 μm, those within the range of ± 5 μm were rated as 〇, those with a line width exceeding ± 5 and within the range of ± 10 μm were marked with Δ, and those with a line width exceeding ± 10 μm were marked with ×. The results are shown in Tables 2 and 3 below.
The line width is controlled so that there is no difference with respect to the set line width, and it can be judged that the patterning accuracy is good.

2. Heat resistance A sample for evaluation was obtained by using the same method as that described in the above section "1. Patterning accuracy".
The film thickness of the obtained pattern was measured, and the film loss rate was calculated by the following formula.
Film loss rate (%) = 100- (Film thickness after post-baking / Film thickness after pre-baking) x 100
The film thickness was measured using DEKTAKXT manufactured by Bruker.
When the film loss rate was less than 20%, it was evaluated as 〇, when it was 20% or more and less than 25%, it was evaluated as Δ, and when it was 25% or more, it was evaluated as ×. The results are shown in Tables 2 and 3 below.
It can be judged that the smaller the film loss rate, the higher the crosslink density of the resist film and the better the heat resistance.

3. 3. Wrinkles Using the evaluation sample obtained by the method described in the above section "1. Patterning accuracy", the presence or absence of wrinkles observed on the surface of the pattern formed with a mask opening of 30 μm was observed by optical microscopy as follows. Evaluation was performed based on the criteria. “Wrinkles” are observed when the film thickness of the obtained pattern is not uniform and there is uneven thickness. Examples of the optical microscope observation image and the SEM observation image when the pattern is wrinkled are shown in FIGS. 1 and 2, and FIG. 4 and FIG. 2 are examples of the optical microscope observation image and the SEM observation image when the pattern is wrinkled. It is shown in FIG. When wrinkles are generated, as shown in FIGS. 1 and 2, a striped pattern presumed to be caused by uneven thickness is observed.
〇: No wrinkles were observed.
Δ: Wrinkles were observed.
If there are no wrinkles, it can be judged that the pattern morphology is good.

4. Storage stability The viscosity of the compositions of Examples and Comparative Examples immediately after production and the viscosity after being left at 23 ° C for 7 days were measured in a viscometer at 25 ° C (cone plate type viscometer (TVE-22H manufactured by Toki Sangyo Co., Ltd.). )) Was measured, and the storage stability was evaluated according to the following criteria.
〇: Viscosity change rate after standing with respect to viscosity immediately after production is less than 10% ×: Viscosity change rate after standing with respect to viscosity immediately after manufacturing is more than 10% When the evaluation is 〇, the storage stability is excellent. Can be confirmed.

From Tables 2 to 4, ^{the compound A in which the thiol group is protected by R 1} has, for example, patterning accuracy and heat resistance as compared with the example in which the thiol compound is used instead of the compound A and the example in which the thiol compound is not contained. It was confirmed that an excellent composition can be formed.
Compound A is a compound represented by the above general formula (A6) such as the above formulas (A6-1) and (A6-2), and the above general formula (A4) such as (A4-1) and (A4-2). It was confirmed that the compound represented by (1) can form a composition having excellent patterning accuracy and heat resistance.
Further, the structure in which R ¹ is substituted with the methylene group at the sulfur atom side terminal by -CO-NR- is more wrinkled than the structure in which the methylene group at the sulfur atom side terminal is substituted with -CO-O-. It was confirmed that the occurrence of was small.
-CO-NR- methylene group of the sulfur atom-side end is replaced structure than -CO-O- in the methylene group of a sulfur atom tail substituted structure, the progress of the elimination reaction of R ¹ As a result of a difference in the progress of the desorption reaction between a place where it is difficult to proceed and the temperature rises easily during heat treatment such as the front surface side of the patterned cured product and a place where the temperature rise is not easy such as the back surface side, the final result is It is presumed that the difference in crosslink density in the obtained patterned cured product becomes large and wrinkles occur.

[Examples 2-23 to 2-28 and Comparative Examples 2-10 to 2-15]
Compound A, thiol compound, polymerizable component B, polymerization initiator, pigment dispersion, coupling agent, and solvent are mixed according to the formulations shown in Tables 5 to 6 below, and the composition is stirred at 25 ° C. for 1 hour. Got
Moreover, the above-mentioned material was used for each component.
The blending amount in the table represents the mass part of each component.

The compounds obtained in Examples and Comparative Examples were evaluated as follows in addition to the evaluation of "1. Patterning accuracy" described above. The results are shown in Tables 5-6.

5. Heat resistance 2
The compositions of Examples and Comparative Examples were spin-coated on a glass substrate so that the film thickness after post-baking was 2 μm, prebaked at 90 ° C. for 120 seconds using a hot plate, and then at 23 ° C. It was cooled for 60 seconds.
Then, it was exposed through a photomask (mask opening 30 μm) using an ultra-high pressure mercury lamp (exposure gap 300 μm, exposure amount 40 mJ / cm ² ).
After developing for 60 seconds using a 0.04 mass% KOH aqueous solution as a developer, wash thoroughly with water, post-bake at 230 ° C. for 20 minutes using a clean oven, fix the pattern, and evaluate a sample with a film thickness of 2 μm. Got
Further, an evaluation sample having a film thickness of 10 μm was obtained in the same manner as described above except that the film thickness after post-baking was spin-coated to be 10 μm.
Using these samples, the film loss rate (%) was calculated in the same manner as in the evaluation of "2. Heat resistance" above. The table shows the numerical value of the film loss rate (%).

6. Wrinkles The same evaluation as in "3. Wrinkles" was performed using the evaluation sample obtained by the method described in the above "5. Heat resistance 2".

7. Development Margin The compositions of Examples and Comparative Examples were spin-coated on a glass substrate so that the film thickness after post-baking was 3 μm, prebaked at 90 ° C. for 120 seconds using a hot plate, and then 23. It was cooled at ° C. for 60 seconds.
Then, it was exposed through a photomask (mask opening 30 μm) using an ultra-high pressure mercury lamp (exposure gap 300 μm, exposure amount 40 mJ / cm ² ).
Using a 0.04 mass% KOH aqueous solution as a developer, spray development was performed at 23 ° C. and a discharge pressure of 0.15 MPa, and the time until the cured portion located at the opening of the mask peeled off from the substrate was measured. , The evaluation was performed according to the following criteria.
◯: The time until peeling was 100 seconds or more from the start of development.
Δ: The time until peeling was 80 seconds or more and less than 100 seconds from the start of development.
X: The time until peeling was more than 60 seconds and less than 80 seconds from the start of development.

From Tables 5 to 6, ^{it can be seen that the compound A in which the thiol group is protected by R 1} can form a composition having excellent patterning accuracy as compared with the example in which the thiol compound is used instead of the compound A. It could be confirmed. In addition, it was confirmed that a composition having excellent heat resistance and development margin and no wrinkles could be formed as compared with the example containing no thiol compound. Since the development margin is excellent, a pattern having a predetermined shape can be stably formed even when the alkaline development time fluctuates.
Compared with the case where A-6 (the compound represented by the above general formula (A3a-1)) is used as the compound A, A-2 (the compound represented by the above general formula (A4-1)) is used. A composition having a better development margin was obtained. Since the protective thiol group equivalent in compound A is A-2> A-6, it is assumed that the crosslink density is higher when A-6 is used. However, since A-2, which is hexafunctional and has a large molecular weight, has high hydrophobicity, a cured product having higher resistance to an alkaline developer can be obtained. As a result, the alkaline developer is better when A-2 is used. It is presumed that a stable cured product was formed even when exposed to the water for a long time.

8. Patterning accuracy 2
The compositions of Examples 2-24, Comparative Examples 2-11 and 2-14 were spin-coated on a glass substrate so that the thickness after prebaking was 4.0 μm to form a coating film. Then, using a hot plate, prebaking was performed at 90 ° C. for 120 seconds, and then cooling was performed at 23 ° C. for 60 seconds. Then, an ultrahigh pressure mercury lamp was used to expose through a photomask with an exposure gap of 300 μm. The exposed coating film was developed with a 0.04 mass% KOH aqueous solution as a developing solution for 60 seconds, washed well with water, and post-baked at 230 ° C. for 20 minutes using a clean oven to fix the pattern. And a sample for evaluation was obtained. The evaluation sample was prepared by combining the following levels as the photomask aperture width and the exposure amount.
Mask opening width (5 levels): 2.0 μm, 10.0 μm, 30.0 μm, 50.0 μm, 100.0 μm
Exposure (3 levels): 50 mJ / cm ² , 100 mJ / cm ² , 300 mJ / cm ²
The obtained pattern was observed with an optical microscope, and the line width corresponding to the mask aperture width was measured. The results are shown in Table 7 below.
The line width is controlled so that there is no difference with respect to the set line width, and it can be judged that the patterning accuracy is good.

9. Heat resistance 3
An evaluation sample was obtained by using the same method as that described in "8. Patterning accuracy 2" above.
The film thickness of the obtained pattern was measured using a DEKTAKXT manufactured by Bruker. The results are shown in Table 7 below.
It can be judged that the heat resistance is so good that there is no difference in the thickness after prebaking.

From Table 7, it was confirmed that by using Compound A, a patterned cured product having a width with a small difference from the mask opening width could be obtained regardless of the amount of exposure.
Further, from Table 7, it was confirmed that by using Compound A, a patterned cured product having a thickness having a small difference from the thickness after prebaking could be obtained regardless of the amount of exposure.
As described above, by using the compound A, a patterned cured product having a set width and thickness can be obtained regardless of the amount of exposure, and a patterned cured product having a high aspect ratio can be stably obtained. I was able to confirm that.

Claims (12)

A compound represented by the following general formula (A).

(In the formula, R ¹ is an aliphatic group having a monovalent carbon atom number of 1 to 40, an aromatic hydrocarbon ring-containing group having a monovalent carbon atom number of 6 to 35, and a monovalent carbon atom number of 2 to 35. Represents a heterocyclic group or a silyl group having a monovalent carbon number of 0 to 40.
X represents an aliphatic group having 1 to 40 carbon atoms having the same number of valences as n, an aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 35 carbon atoms. ,
One or more of the methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocyclic group and silyl group are -O-, -S-, -CO- and -O-CO-. , -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-,- Is it sometimes replaced with a group selected from NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -S-S- or -SO _2-? , Or may be replaced by a group that combines these groups under the condition that the oxygen atoms are not adjacent to each other.
n represents an integer of 2 or more and 10 or less. ) The compound according to claim 1, which is represented by the following general formulas (A1), (A2), (A3), (A4), (A5) or (A6).

(In the formula, R ¹¹ and R ¹² independently represent the following general formula (101).
L ¹¹ and L ¹² represent an alkylene group having 1 to 10 carbon atoms.
a1 represents an integer of 1 to 20 and represents
R ²¹ , R ²² and R ²³ independently represent the following general formula (101) or (102), respectively.
Any two or more of R ²¹ , R ²² and R ²³ have the following general formula (101).
L ²¹ , L ²² and L ²³ represent an alkylene group having 1 to 10 carbon atoms.
R ²⁴ represents an aliphatic group having a hydrogen atom or a monovalent carbon atom number of 1 to 40.
R ³¹ , R ³² , R ³³ and R ³⁴ independently represent the following general formula (101) or (102).
Any two or more of R ³¹ , R ³² , R ^33, and R ³⁴ have the following general formula (101).
L ³¹ , L ³² , L ³³ and L ³⁴ represent an alkylene group having 1 to 10 carbon atoms.
R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ independently represent the following general formula (101) or (102), respectively.
Any two or more of R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ is the following general formula (101).
L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ and L ⁴⁶ represent an alkylene group having 1 to 10 carbon atoms.
R ⁵¹ , R ⁵² and R ⁵³ independently represent the following general formula (101) or (102), respectively.
Any two or more of R ⁵¹ , R ^52, and R ⁵³ have the following general formula (101).
L ⁵¹ , L ⁵² and L ⁵³ represent an alkylene group having 1 to 10 carbon atoms.
R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ independently represent the following general formula (101) or (102).
Any two or more of R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ is the following general formula (101).
L ⁶¹ , L ⁶² , L ⁶³ and L ⁶⁴ represent an alkylene group having 1 to 10 carbon atoms.
R ⁶⁵ and R ⁶⁶ each independently represent a hydrogen atom or an aliphatic group having 1 to 40 monovalent carbon atoms.
One or more of the methylene groups in the aliphatic group are -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-,-. S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -O- It may have been replaced with a group selected from CO-NH-, -NR'-, -S-S- or -SO _2- , or these groups were combined under the condition that the oxygen atoms were not adjacent to each other. May have been replaced by a group. )

(In the formula, R ¹ is an aliphatic group having a monovalent carbon atom number of 1 to 40, an aromatic hydrocarbon ring-containing group having a monovalent carbon atom number of 6 to 35, and a monovalent carbon atom number of 2 to 35. Represents a heterocyclic group or a silyl group having a monovalent carbon number of 0 to 40.
* Indicates the joint location
One or more of the methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocyclic group and silyl group are -O-, -S-, -CO- and -O-CO-. , -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-,- Is it sometimes replaced with a group selected from NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -S-S- or -SO _2-? , Or the oxygen atoms may be replaced with a combined group of these groups under the condition that they are not adjacent to each other. ) ^{All of R 21} , R ²² and R ^{23 in} the general formula (A2) are independently the general formula (101).
^{All of R 31} , R ³² , R ³³ and R ^{34 in} the general formula (A3) are independently the general formula (101).
^{All of R 41} , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ^{46 in} the general formula (A4) are independently the general formula (101).
^{All of R 51} , R ⁵² and R ⁵³ in the general formula (A5) are independently the general formula (101).
^{The compound according to claim 2, wherein all of R 61} , R ⁶² , R ⁶³ and R ^{64 in} the general formula (A6) are independently of the general formula (101). The compound according to claim 2 or 3, which is represented by the general formula (A4) or (A6). R ¹ is an aliphatic group having 1 to 40 monovalent carbon atoms or 6 monovalent carbon atoms in which the methylene group at the end on the sulfur atom side is substituted with -CO-O- or -CO-NR-. The compound according to any one of claims 1 to 4, which is an aromatic hydrocarbon ring-containing group of ~ 35. A thiol generator containing the compound according to any one of claims 1 to 5. The thiol generator according to claim 6, which is used for pattern formation. Compounds represented by the following general formula (A) and
With a thiol-reactive polymerizable component,
Composition having.

(In the formula, R ¹ is an aliphatic group having a monovalent carbon atom number of 1 to 40, an aromatic hydrocarbon ring-containing group having a monovalent carbon atom number of 6 to 35, and a monovalent carbon atom number of 2 to 35. Represents a heterocyclic group or a silyl group having a monovalent carbon number of 0 to 40.
X represents an aliphatic group having 1 to 40 carbon atoms having the same number of valences as n, an aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 35 carbon atoms. ,
One or more of the methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, heterocyclic group and silyl group are -O-, -S-, -CO- and -O-CO-. , -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-,- Is it sometimes replaced with a group selected from NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -S-S- or -SO _2-? , Or may be replaced by a group that combines these groups under the condition that the oxygen atoms are not adjacent to each other.
n represents an integer of 2 or more and 10 or less. ) The composition according to claim 8, wherein the thiol-reactive polymerizable component contains a radically polymerizable compound. A cured product of the composition according to claim 8 or 9. The method for producing a cured product according to claim 10.
A method for producing a cured product, which comprises a step of cross-linking the polymerizable components having thiol reactivity with the compound represented by the general formula (A). The method for producing a cured product according to claim 11, further comprising a step of polymerizing the polymerizable components having thiol reactivity with each other.

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